Extraction of target materials using czts sorbent

ABSTRACT

Various embodiments disclosed relate to extraction of target materials using a CZTS sorbent. A method of extracting a target material from a medium includes contacting a copper zinc tin sulfur (CZTS) sorbent with the target material in the medium including the target material to form a used CZTS sorbent that includes the target material.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. Utility application Ser. No. 16/890,076 filed on Jun. 2, 2020, which is a continuation-in-part of and claims the benefit of priority under 35 U.S.C. § 120 to U.S. Utility application Ser. No. 16/661,862 filed on Oct. 23, 2019, which is a continuation-in-part of U.S. Utility application Ser. No. 16/042,840 filed Jul. 23, 2018, which is a continuation-in-part of U.S. patent application Ser. No. 15/606,704, filed on May 26, 2017, which is a continuation-in-part of U.S. patent application Ser. No. 14/808,563, filed on Jul. 24, 2015, which claims the benefit of U.S. Provisional Application No. 62/029,041, filed Jul. 25, 2014 and U.S. Provisional Application No. 62/133,791, filed Mar. 16, 2015, the disclosures of which are incorporated herein in their entirety by reference.

BACKGROUND

This section provides background information related to the present disclosure which is not necessarily prior art.

Many industries from numerous sectors of the economy have emissions of one kind or another. Such emissions can be separated into two basic groups, one being gaseous and the other being non-gaseous. It is common for emissions in the gaseous group and emissions in the non-gaseous group to contain hazardous contaminants. Emissions in the gaseous group may be in the form of exhaust gases generated by a coal fired plant or from a natural gas burning facility. Emissions in the non-gaseous group may be in the form of liquid-like, sludge-like, or slurry-like substances. If and when the level of hazardous contaminants in emissions meets and/or exceeds allowable limits, the contaminants must either be neutralized, captured, collected, removed, disposed of, and/or properly contained by one means or another.

Many industries rely upon burning a fuel material as a means to accomplish some aspect of their respective process. For instance, in a first example, steel mills burn and/or smelt metal in the process of making metal shapes, extrusions, and other metal castings. The processes used in the metal industry include operations in which particulates are emitted in metallic vapor and ionized metal. Hazardous contaminants to the environment, plants, animals, and/or humans are released into the air via the metallic vapor. To one degree or another, the hazardous contaminants in the metallic vapor and/or the metallic vapor compounds must be collected and disposed of properly. In a second example, the industry of mining precious heavy metals such as gold, silver, and platinum includes metals and metallic vapor emissions containing heavy metal contaminants and particulates that are considered hazardous if not captured, collected, and disposed of properly. In a third example, industries burning natural gas have emissions that often contain elevated levels of contaminants that are considered to be hazardous if not captured, collected, and disposed of properly. In a fourth example, the producers of energy who use coal as a burnable consumable to create steam in boilers for turning generators have considerable emissions containing metallic vapor and metallic compounds that are considered hazardous to the environment, plants, animals, and humans. Among other hazardous contaminants, metallic vapor emissions often contain mercury (Hg).

Because of the pattern of global jet streams, airborne metallic vapor emissions may be carried from one country and deposited in another. For instance, it is possible that much of the emissions of mercury generated in China and/or India may actually end up being deposited in the USA and/or the ocean waters in between. In a similar fashion, much of the mercury laden emissions generated in the USA may actually be deposited in Europe and/or in the ocean waters in between. To complete this circle, much of the mercury laden emissions generated in Europe may actually be deposited in China and/or India. Therefore, the containment of mercury and other hazardous contaminants in emissions generated by industrial processes is a global problem with global implications requiring a global effort to resolve it.

National and international regulations, rules, restrictions, fees, monitoring, and a long line of ever evolving and increasingly stringent laws are proposed and/or enforced upon those generating such emissions. For example, one of the most egregious and regulated contaminants in metallic vapor emissions is mercury. Human industrial processes have greatly increased the accumulation of mercury and/or mercury deposits in concentrations that are well above naturally occurring levels. On a global basis, it is estimated that the total quantity of mercury released by human-based activities is as much as 1,960 metric tons per year. This figure was calculated from data analyzed in 2010. Worldwide, the largest contributors to this particular type of emission are coal burning (24%) and gold mining (37%) activities. In the USA, coal burning accounts for a higher percentage of emissions than gold mining activities.

The primary problem with exposure to mercury for animals and humans is that it is a bioaccumulation substance. Therefore, any amount of mercury ingested by fish or other animals remains in the animal (i.e. accumulates) and is passed on to humans or other animals when the former is ingested by the later. Furthermore, the mercury is never excreted from the body of the ingesting host. In the food chain, larger predators, which either live the longest and/or eat large quantities of other animals, are at the greatest risk of having excessive mercury accumulations. Humans, who eat too much mercury-laden animals, especially fish, are subject to a wide range of well-known medical issues including nervous system maladies and/or reproductive problems.

There are three primary types of mercury emissions: anthropogenic emissions, re-emission, and naturally occurring emissions. Anthropogenic emissions are mostly the result of industrial activity. Anthropogenic emission sources include industrial coal burning plants, natural gas burning facilities, cement production plants, oil refining facilities, the chlor-alkali industry, vinyl chloride industry, mining operations, and smelting operations. Re-emissions occur when mercury deposited in soils is re-dispersed via floods or forest fires. Mercury absorbed in soil and/or deposited in soil can be released back into the water via rain runoff and/or flooding. As such, soil erosion contributes to this problem. Forest fires, whether they are acts of nature, arson, or deliberate deforestation burning, re-emits mercury back into the air and/or water sources only to be deposited again elsewhere. Naturally occurring emissions include volcanoes and geothermal vents. It is estimated that about half of all mercury released into the atmosphere is from naturally occurring events such as volcanos and thermal vents.

As noted above, coal burning plants release a large quantity of mercury and other contaminants into the environment each year. Accordingly, there are many ongoing efforts to reduce the amount of hazardous contaminants in the flue gas emissions produced by coal burning plants. Many coal burning plants in the USA are equipped with emissions control systems which capture, contain, and/or recover hazardous elements such as mercury. In coal burning plants, coal is burned to boil water, turning the water into steam, which is used to run electric generators. The flue gas emissions from the burning of coal are often conveyed through a conduit system to a fluid gas desulfurization unit and/or a spray dryer system, which remove some emissions and some of the noxious fumes such as sulfur dioxide (SO₂) and hydrogen chloride (HCl) from the flue gases. A typical conduit system then routes the flow of flue gases to a wet or dry scrubber where more sulfur dioxide, hydrogen chloride, and fly ash are removed. The flow of flue gases is routed through a bag house where particulates are separated from the airflow in the flue gases, similar to the way a household vacuum cleaner bag works. The flue gases pass through the filter-like bags, which have a porosity allowing airflow but not the larger particulates traveling in the airflow. The surfaces of the filter bags are shaken and/or cleaned to collect the captured particulates so that they can be disposed of. Usually, these deposits are hazardous emissions themselves and must be disposed of accordingly. The balance of flue gasses that make it through this type of emissions control system is then allowed to escape through a tall smoke stack and released into the atmosphere.

The problem with this type of emissions control system is that it is virtually ineffective to capture and/or collect the heavy metals such as mercury contained in a metallic vapor and metallic compound vapor form. Since the coal fired burning systems burn coal at relatively elevated temperatures near 1,500 degrees Fahrenheit, the mercury is converted into nano-sized vapor particles that are able to slip through even the most capable filter systems. As a result, significant emissions of air borne mercury and other hazardous contaminants are released into the atmosphere.

In an effort to capture and collect mercury from coal fired systems and/or other emission sources of mercury, several known systems have been developed to address the problem, which generally fall into one of three categories.

The first category is a group of methods and/or systems that capture mercury by injecting a sorbent into the flue gas stream. Other than a noble metal, the most common sorbent material used is activated carbon and/or biochar. Activated carbon is often halogenated with bromine. Biochar is a form of charcoal and is rich in carbon. The injection of sorbents into the flue gas helps to capture contaminants in one and/or any combination of the following typical emissions control devices: an electrostatic precipitator, a fluidized gas desulfurization system, scrubber systems, or fabric filter systems. There are several variations of these systems, requiring the injection of activated carbon at various points of the emission control system after combustion of the coal. Some exemplary methods and/or systems of the first category are disclosed in U.S. Pat. Nos. 7,578,869, 7,575,629, 7,494,632, 7,306,774, 7,850,764, 7,704,920, 7,141,091, 6,905,534, 6,712,878, 6,695,894, 6,558,454, 6,451,094, 6,136,072, 7,618,603, 7,494,632, 8,747,676, 8,241,398, 8,728,974, 8,728,217, 8,721,777, 8,685,351, and 8,029,600.

The second category is a group of methods and/or systems that pretreat the coal fuel before combustion in an effort to reduce the levels of mercury in the coal fuel. Some exemplary methods and/or systems of the second category are described in U.S. Pat. Nos. 7,540,384, 7,275,644, 8,651,282, 8,523,963, 8,579,999, 8,062,410, and 7,987,613. All of the methods and/or systems set forth in these exemplary patents generate large volumes of unusable coal, which is also considered a hazardous waste. As a result, the methods and/or systems of the second category of known solutions are inefficient and expensive to operate. Furthermore, substantial capital and physical space is often required for the pretreatment of coal, making it impractical to retrofit many existing emission control systems with the necessary equipment.

The third category is a group of methods and/or systems that inject a catalyst into the emissions control equipment upstream of the activated carbon injection system. The catalyst in these methods and/or systems ionize the mercury making it easier to collect and remove the mercury from the flue gasses. However, the efficiency of such methods and/or systems is poor and operating costs are high, such that the methods and/or systems of the third category of known solutions are not cost effective. Examples of the third category of are described in U.S. Pat. Nos. 8,480,791, 8,241,398, 7,753,992, and 7,731,781. In addition to these examples, U.S. Pat. No. 7,214,254 discloses a method and apparatus for regenerating expensive sorbent materials by using a microwave and a fluid bed reactor. The method selectively vaporizes mercury from the sorbent, at which point the mercury can be caught in a specialized filter or condensed and collected. The use of microwave generation renders this method impractical for large scale commercial applications and is therefore only useful for the regeneration of expensive sorbents. Another example is found in U.S. Patent Application Publication No. 2006/0120935, which discloses a method for the removal of mercury from flue gasses using any one of several substrate materials to form chemical attractions to the mercury as the flue gasses pass through the emissions control equipment. This method is also impractical for large scale commercial use. Therefore, current emissions control systems and methods generally operate by transferring the hazardous contaminants from a gaseous emission to a non-gaseous emission, which creates another set of emission control problems.

While many laws and regulations focus on metallic vapor emissions, other forms of emissions containing hazardous contaminants such as slurry and/or slurry-like emissions, sludge and/or sludge-like emissions, liquid and/or liquid-like emissions, and other emission variations should not be overlooked. All of the emission types listed may also require processing where the hazardous contaminants they contain can be neutralized, captured, collected, removed, disposed of, and/or properly contained by one means or another. Historically, the most cost effective and most widely used process for removing hazardous contaminants utilizes activated carbon (in one form or another), through which the emissions pass. Accordingly, the demand for activated carbon in the USA is expected to grow each year through 2017 with over one billion pounds required each and every year at a cost to industries of over $1-1.50/pound. This equates to about $1 billion annually. Most of the projected increase in demand for activated carbon is driven by the implementation of EPA promulgated regulations, which require utilities and industrial manufacturers to upgrade coal-fired power plants to comply with ever more stringent requirements.

In addition to the ever more stringent gaseous emissions regulations, the EPA has implemented tougher regulations for non-gaseous emissions through The Clean Water Act, which must be fully complied with by 2016. The combination of increasing regulations on all types of emissions impacts multiple types of emissions that are produced by a variety of different industries. Some industries, such as electrical power producers, who burn fuel to generate power, produce primary gaseous emissions containing hazardous contaminants. Per industry standards, these gaseous emissions are exposed to activated carbon materials in an effort to capture enough volume of hazardous contaminants so as to render the gaseous emission at or below allowable limits for contaminants. The process of removing the hazardous contaminants from the gaseous emissions generated from burning these fuels results in and/or generates secondary non-gaseous emissions in the form of liquid-like or slurry-like substances containing the hazardous contaminants. The hazardous contaminants in the second non-gaseous emissions must also be captured and/or contained appropriately to prevent the hazardous contaminants from being discharged into the environment. Both the primary gaseous emissions and the secondary non-gaseous emissions require a means of properly capturing and/or reclaiming and/or confining enough of the hazardous contaminants to comply with environmental regulations. The industrial costs associated with known available processes capable of accomplishing the removal of the hazardous contaminants from the secondary non-gaseous emissions are almost so cost prohibitive that some industries are forced to shut down facilities if they cannot pass the costs along to consumers.

In accordance with some practices, non-gaseous emissions, which are considered to be hazardous because they contain elevated levels of contaminants, are consigned and contained for long-term storage in ponds, piles, or drying beds. While such practices isolate the hazardous contaminants, they are expensive and consume land area without neutralizing the hazardous contaminants themselves, which can result in environmental hazards at the containment sites. One example of a non-gaseous emission is fly ash, which is a naturally-occurring product from the combustion of coal. Fly ash is basically identical in composition to volcanic ash. Fly ash contains trace concentrations (i.e. amounts) of many heavy metals and other known hazardous and toxic contaminants including mercury, beryllium, cadmium, barium, chromium, copper, lead, molybdenum, nickel, radium, selenium, thorium, uranium, vanadium, and zinc. Some estimates suggest that as much as 10% of the coal burned in the USA consists of unburnable material, which becomes ash. As a result, the concentrations of hazardous trace elements in coal ash are as much as 10 times higher than the concentration of such elements in the original coal.

Fly ash is considered to be a pozzolan material with a long history of being used in the production of concrete because when it is mixed with calcium hydroxide a cementitious material is formed that aggregates with water and other compounds to produce a concrete mix well suited for roads, airport runways, and bridges. The fly ash produced in coal burning plants is flue-ash that is comprised of very fine particles which rise with the flue gases. Ash that does not rise is often called bottom ash. In the early days of coal burning plants, fly ash was simply released into the atmosphere. In recent decades, environmental regulations have required emission controls to be installed to prevent the release of fly ash into the atmosphere. In many plants the use of electrostatic precipitators capture the fly ash before it can reach the chimneys and exit to atmosphere. Typically the bottom ash is mixed with the captured fly ash to form what is known as coal ash. Usually, the fly ash contains higher levels of hazardous contaminants than the bottom ash, which is why mixing bottom ash with fly ash brings the proportional levels of hazardous contaminants within compliance of most standards for non-gaseous emissions. However, future standards may reclassify fly ash as a hazardous material. If fly ash is reclassified as a hazardous material it will be prevented from being utilized in the production of cement, asphalt, and many other widely used applications. It has been estimated by some studies that the cost increase of concrete in the USA alone would exceed $5 billion per year as a result of a ban on the usage of fly ash in concrete production. The increase in cost is a direct result of more expensive alternative materials being used in place of fly ash. In addition, no other known material is suitable as a direct replacement for fly ash in cement due to its unique physical properties.

Reports indicate that in the USA over 130 million tons of fly ash is produced annually by over 450 coal-fired power plants. Some reports estimate that barely 40% of this fly ash is re-used, indicating that as much as 52 million annual tons of fly ash is reused leaving as much as 78 million annual tons stored in bulk in slurry ponds and piles. Fly ash is typically stored in wet slurry ponds to minimize the potential of fugitive particulates becoming airborne, which could convey contaminants out of bulk storage and into the atmosphere and surrounding environment. In addition to airborne releases of bulk storage fly ash, there is a threat of breach and/or failure of the containment systems required for the long term containment of fly ash. One famous example of a breach occurred in 2008 in Tennessee, where an embankment of a wet storage fly ash pond collapsed, spilling 5.4 million cubic yards of fly ash. The spill damaged several homes and contaminated a nearby river. Cleanup costs are still ongoing at the time of this application and could exceed $1.2 billion.

In another example, non-gaseous emissions may be found as byproducts in typical wastewater generation systems of coal burning facilities. In typical wastewater generation systems, large volumes of water come from boiler blow down and cooling water processes. These large volumes of wastewater contain relatively low levels of contaminants and are used to dilute other waste streams containing much higher levels of contamination. The contaminated wastewater streams typically discharged from scrubber systems is diluted with the large volumes of wastewater from the boiler blow down and/or cooling water processes and then treated in large continuous mix tanks with lime to form gypsum, which is then pumped into settling ponds. During this process certain amounts of mercury and other heavy metals are entrained with the gypsum and stabilized for use in wallboard and cement. This gypsum is generally considered to be non-leaching and is not considered a pollution hazard. However, the water from the settling ponds is generally discharged into the waterways. Current regulations allow this ongoing discharge, but looming regulations propose that certain contaminants and/or levels of those contaminants be mandated as a hazardous pollution.

With regard to removing mercury and heavy metals from non-gaseous industrial wastewater streams, the use of carbonate, phosphate, or sulfur is often employed in an effort to reduce hazardous contaminants to low residual levels. One known method for removing mercury and other hazardous contaminants from industrial wastewater streams is chemical precipitation reaction. Another known method utilizes ion exchange. One of the primary problems with the chemical precipitation reaction and ion exchange methods is that these methods are not sufficient to fully comply with the ever more stringent EPA regulations for non-gaseous emissions when the amount of contaminants is high, such as for treating fly ash slurry emissions.

Another source of contaminated non-gaseous emissions is from maritime vessels waste discharge and/or ballast discharge. Commercial ships such as cargo ships and tankers have both waste and ballast discharge. Entertainment cruise liners also have discharge effluents to deal with at port stops. Additionally, military and defense vessels have significant discharge effluents.

Another significant discharge effluent is generated by offshore drilling operations. Treatment of effluent waste on-site at the offshore rig is much less expensive than transportation of waste to land for treatment. Therefore, efficient filtering of offshore waste prior to discharge into the sea is necessary to maintain appropriate and acceptable ecology requirements. Virtually all contaminated emissions applications vary in the types and/or specific concentrations of contaminates in the emissions. Therefore, a one-size-fits-all approach for a suitable sorbent which is optimized for all possible contaminated emissions applications is not possible. There is a need for providing application specific sorbent solutions for optimizing effective emissions control based on specific contaminates resident in emissions. A further need exists to be able to adjust the sorbent application during use to correspond to changing levels and/or types of contaminates resident in the emissions.

There are also various known commercial emissions control methods and systems sold under different tradenames for treating secondary non-gaseous emissions. One treatment method known by the tradename Blue PRO is a reactive filtration process that removes mercury from secondary non-gaseous emissions using co-precipitation and absorption. Another treatment method known by the tradename MERSORB-LW uses a granular coal based absorbent to remove mercury from secondary non-gaseous emissions by co-precipitation and absorption. Another treatment method known as Chloralkali Electrolysis Wastewater removes mercury from secondary non-gaseous emissions during the electrolytic production of chlorine. Another treatment method uses absorption kinetics and activated carbon derived from fertilizer waste to remove mercury from secondary non-gaseous emissions. Another treatment method uses a porous cellulose carrier modified with polyethyleneimine as an absorbent to remove mercury from secondary non-gaseous emissions. Another treatment method uses microorganisms in an enzymatic reduction to remove mercury from secondary non-gaseous emissions. Yet another treatment method known by the tradename MerCUR_(x)E uses chemical precipitation reactions to treat contaminated liquid-like non-gaseous emissions.

A common treatment method by some of the emissions control systems is to dilute contaminates instead of removing them from the emissions. As a result, if the PPM levels of a contaminate in an emission exceeds the allowable levels, then rather than removing the contaminate to reduce the level, additional non-contaminated volume is added to the emission so that the resulting PPM levels are reduced to allowable levels, even though the actual amount of contaminate being allowed remains unchanged. There is a serious need to overcome this practice of dilution by providing an effective emissions control method which not only reduces the PPM level of contaminates, but removes the contaminates from the emissions.

SUMMARY OF THE INVENTION

In various embodiments, the present invention provides a method of extracting a target material from a medium. The method includes contacting a copper zinc tin sulfur (CZTS) sorbent with the target material in the medium including the target material to form a used CZTS sorbent that includes the target material.

In various embodiments, the present invention provides a method of extracting a target material from a medium. The method includes contacting a copper zinc tin sulfur (CZTS) sorbent with the target material in the medium including the target material to form a used CZTS sorbent that includes the target material. The target material includes a metal, a heavy metal, a precious metal, a rare earth metal, a rare metal, an alkali metal, a transition metal, an alkaline earth metal, a metalloid, selenium, selenite, selenate, sulfur, nitrogen, nitrogen dioxide, nitrate, nitrite, phosphorus, phosphate, phosphite, sulfur, sulfur dioxide, ammonia, boron, a halogen, mercury, mercury oxide, a compound thereof, a complex thereof, a salt thereof, an organic solvent, or a combination thereof. The medium includes a medium used in or obtained from a mining operation.

In various embodiments, the present invention provides a method of extracting a target material from a medium. The method includes contacting a copper zinc tin sulfur (CZTS) sorbent with the target material in the medium including the target material to form a used CZTS sorbent that includes the target material. The target material includes a metal, a heavy metal, a precious metal, a rare earth metal, a rare metal, an alkali metal, a transition metal, an alkaline earth metal, a metalloid, selenium, selenite, selenate, sulfur, nitrogen, nitrogen dioxide, nitrate, nitrite, phosphorus, phosphate, phosphite, sulfur, sulfur dioxide, ammonia, boron, a halogen, mercury, mercury oxide, a compound thereof, a complex thereof, a salt thereof, an organic solvent, or a combination thereof. The medium is a medium from a combustion process in a power plant.

In various embodiments, the present invention provides a method of forming a CZTS sorbent. The method includes combining copper, a compound thereof, or a salt thereof; zinc, a compound thereof, or a salt thereof; tin, a compound thereof, or a salt thereof; and sulfur, a compound thereof, or a salt thereof; to form a starting material mixture. The method also includes processing the starting material mixture under conditions suitable to form the CZTS sorbent.

BRIEF DESCRIPTION OF THE FIGURES

The drawings illustrate generally, by way of example, but not by way of limitation, various embodiments of the present invention.

FIG. 1 is a schematic diagram illustrating a known layout for a coal burning power plant;

FIG. 2 is a schematic diagram illustrating a known layout for an emissions control system used to remove contaminants from emissions produced by coal burning power plants of the type shown in FIG. 1;

FIG. 3 is a schematic diagram of the emissions control system shown in FIG. 2 where the emissions control system has been modified by the adding an exemplary reverse venturi apparatus that is constructed in accordance with the subject disclosure;

FIG. 4A is a side cross-sectional view of an exemplary reverse venturi apparatus constructed in accordance with the subject disclosure, which includes a housing having an entry portion, an enlarged portion, and an exit portion;

FIG. 4B is a front cross-sectional view of the entry portion of the housing of the exemplary reverse venturi apparatus illustrated in FIG. 4A;

FIG. 4C is a front cross-sectional view of the enlarged portion of the housing of the exemplary reverse venturi apparatus illustrated in FIG. 4A;

FIG. 4D is a front cross-sectional view of the exit portion of the housing of the exemplary reverse venturi apparatus illustrated in FIG. 4A;

FIG. 5 is a side cross-sectional view of another exemplary reverse venturi apparatus constructed in accordance with the subject disclosure where a series of staggered baffles are disposed in the enlarged portion of the housing creating a serpentine shaped flow path for the emissions;

FIG. 6A is a side cross-sectional view of another exemplary reverse venturi apparatus constructed in accordance with the subject disclosure where an auger-shaped baffle is disposed in the enlarged portion of the housing creating a helically shaped flow path for the emissions;

FIG. 6B is a front perspective view of the auger-shaped baffle illustrated in the exemplary reverse venturi apparatus shown in FIG. 6A;

FIG. 7A is a side cross-sectional view of another exemplary reverse venturi apparatus constructed in accordance with the subject disclosure where a plurality of spaced apart baffles are disposed in the enlarged portion of the housing;

FIG. 7B is a front cross-sectional view of the exemplary reverse venturi apparatus illustrated in FIG. 7A taken along section line A-A where orifices in one of the baffles are shown;

FIG. 8 is a side cross-sectional view of another exemplary reverse venturi apparatus constructed in accordance with the subject disclosure where a plurality of fragments are disposed in the enlarged portion of the housing,

FIG. 9 is a side cross-sectional view of another exemplary reverse venturi apparatus constructed in accordance with the subject disclosure where a plurality of entangled strands are disposed in the enlarged portion of the housing forming a wool-like material therein;

FIG. 10 is a side cross-sectional view of another exemplary reverse venturi apparatus constructed in accordance with the subject disclosure where a filter element is disposed in the enlarged portion of the housing;

FIG. 11 is a side cross-sectional view of another exemplary reverse venturi apparatus constructed in accordance with the subject disclosure where the enlarged portion of the housing contains a plurality of baffles and a plurality of fragments of varying sizes that are disposed in between adjacent baffles;

FIG. 12A is a front elevation view showing one exemplary size of the fragments contained in the enlarged portion of the housing of the exemplary reverse venturi apparatus illustrated in FIG. 11;

FIG. 12B is a front elevation view showing another exemplary size of the fragments contained in the enlarged portion of the housing of the exemplary reverse venturi apparatus illustrated in FIG. 11;

FIG. 12C is a front elevation view showing another exemplary size of the fragments contained in the enlarged portion of the housing of the exemplary reverse venturi apparatus illustrated in FIG. 11;

FIG. 12D is a front elevation view showing another exemplary size of the fragments contained in the enlarged portion of the housing of the exemplary reverse venturi apparatus illustrated in FIG. 11;

FIG. 13A is a front elevation view showing one exemplary piece of loose material with an asterisk-like shape that in combination with other pieces may be used to replace the fragments shown in the exemplary reverse venturi apparatus illustrated in FIGS. 8 and 11;

FIG. 13B is a front elevation view showing one exemplary crystalline flake that in combination with other crystalline flakes may be used to replace the fragments shown in the exemplary reverse venturi apparatus illustrated in FIGS. 8 and 11;

FIG. 13C is a front elevation view showing one exemplary wire coil that in combination with other wire coils may be used to replace the fragments shown in the exemplary reverse venturi apparatus illustrated in FIGS. 8 and 11;

FIG. 14 is a side cross-sectional view showing another exemplary reverse venturi apparatus constructed in accordance with the subject disclosure that includes two separate enlarged portions that are joined together in series;

FIG. 15 is a side cross-sectional view showing another exemplary reverse venturi apparatus constructed in accordance with the subject disclosure that includes two separate enlarged portions that are joined together in parallel;

FIG. 16 is a side cross-sectional view showing another exemplary reverse venturi apparatus constructed in accordance with the subject disclosure;

FIG. 17 is a block flow diagram illustrating a known method for removing contaminants from gaseous emissions;

FIG. 18A is a block diagram illustrating the method for removing contaminants from gaseous emissions illustrated in FIG. 17 where the method has been modified by adding steps for injecting a sorbent into the gaseous emissions at a first introduction point and subsequently passing the gaseous emissions through a reverse venturi apparatus;

FIG. 18B is a block diagram illustrating the method for removing contaminants from gaseous emissions illustrated in FIG. 17 where the method has been modified by adding steps for injecting the sorbent into the gaseous emissions at a second introduction point and subsequently passing the gaseous emissions through the reverse venturi apparatus;

FIG. 19 is a block diagram illustrating a known method for removing contaminants from non-gaseous emissions that calls for depositing the non-gaseous emissions in a settling pond;

FIG. 20 is a block diagram illustrating the method for removing contaminants from non-gaseous emissions illustrated in FIG. 19 where the method has been modified by adding steps for treating a portion of the non-gaseous emissions extracted from the settling pond with a sorbent;

FIG. 21 is a graph illustrating the percentage of contaminants removed from emissions by known emissions control systems and the percentage of contaminants removed from emissions by the apparatus and methods disclosed herein;

FIG. 22 is block flow diagram illustrating an exemplary method of using a reverse venturi shaped fluidized bed apparatus to remove contaminates from gaseous emissions and clean the reactive material that separates the contaminates from the gaseous emissions;

FIG. 23 is block flow diagram illustrating an exemplary method of using a reverse venturi shaped fluidized bed apparatus to remove contaminates from non-gaseous emissions and clean the reactive material that separates the contaminates from the non-gaseous emissions;

FIG. 24 is a flow diagram illustrating extended non-turbulent emissions flow through an exemplary reverse venturi shaped fluidized bed apparatus and exemplary method steps for cleaning and recycling the sorbent that separates the contaminates from the emissions;

FIG. 25 is block flow diagram illustrating an exemplary method using a reverse venturi shaped fluidized bed apparatus with a tilting mechanism mounted to a transportable platform deck where the housing of the reverse venturi shaped fluidized bed apparatus is oriented relatively parallel to the platform deck in order to remove contaminates from gaseous emissions;

FIG. 26 is block flow diagram illustrating an exemplary method using a reverse venturi shaped fluidized bed apparatus with a tilting mechanism mounted to a transportable platform deck where the housing of the reverse venturi shaped fluidized bed apparatus is oriented relatively transverse to the platform deck in order to remove contaminates from non-gaseous emissions;

FIG. 27 is a matrix showing specific types of contaminates matched against the effectiveness of the disclosed CZTS Alloy sorbents compared to activated carbon and zeolite sorbents for gaseous and non-gaseous emissions;

FIG. 28 is a schematic diagram showing specific CZTS Alloy sorbents compared to other specific types of sorbents for gaseous and non-gaseous emissions;

FIG. 29 is a matrix showing prior art sorbents and their ability to separate from contaminates in gaseous and non-gaseous emissions and be reused;

FIG. 30 is a matrix showing the disclosed broad-spectrum CZTS Alloy sorbents and their ability to separate from contaminates in gaseous and non-gaseous emissions and be reused;

FIG. 31 is a block diagram showing a method routing contaminated gaseous emissions through different filters containing specific effective sorbents that match the types and/or levels of contaminates resident in the gaseous emissions;

FIG. 32 is a block diagram showing a method routing contaminated non-gaseous emissions through different filters containing specific effective sorbents that match the types and/or levels of contaminates resident in the non-gaseous emissions; and

FIG. 33 is a flow diagram illustrating extended non-turbulent emissions flow through an exemplary reverse venturi shaped fluidized bed apparatus and exemplary method steps for cleaning and recycling the sorbent that separates the contaminants from the emissions by using a series of sorbent recycling subsystems for CZTS sorbents, CZTS-Alloy sorbents, and/or CZTS-Mixture sorbents.

DETAILED DESCRIPTION OF THE INVENTION

Reference will now be made in detail to certain embodiments of the disclosed subject matter. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter.

Throughout this document, values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of “about 0.1% to about 5%” or “about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The statement “about X to Y” has the same meaning as “about X to about Y,” unless indicated otherwise. Likewise, the statement “about X, Y, or about Z” has the same meaning as “about X, about Y, or about Z,” unless indicated otherwise.

In this document, the terms “a,” “an,” or “the” are used to include one or more than one unless the context clearly dictates otherwise. The term “or” is used to refer to a nonexclusive “or” unless otherwise indicated. The statement “at least one of A and B” or “at least one of A or B” has the same meaning as “A, B, or A and B.” In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that particular section.

In the methods described herein, the acts can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.

The term “about” as used herein can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range, and includes the exact stated value or range.

The term “substantially” as used herein refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%. The term “substantially free of” as used herein can mean having none or having a trivial amount of, such that the amount of material present does not affect the material properties of the composition including the material, such that about 0 wt % to about 5 wt % of the composition is the material, or about 0 wt % to about 1 wt %, or about 5 wt % or less, or less than, equal to, or greater than about 4.5 wt %, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001 wt % or less, or about 0 wt %.

Referring to the Figures, wherein like numerals indicate corresponding parts throughout the several views, an apparatus and methods for removing contaminants from industrial emissions are illustrated.

Example embodiments will now be described more fully with reference to the accompanying drawings. Example embodiments are provided so that this disclosure will be thorough, and will fully convey the scope to those who are skilled in the art. Numerous specific details are set forth such as examples of specific components, devices, and methods, to provide a thorough understanding of embodiments of the present disclosure. It will be apparent to those skilled in the art that specific details need not be employed, that example embodiments may be embodied in many different forms and that neither should be construed to limit the scope of the disclosure. In some example embodiments, well-known processes, well-known device structures, and well-known technologies are not described in detail.

The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting. As used herein, the singular forms “a,” “an,” and “the” may be intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms “comprises,” “comprising,” “including,” and “having,” are inclusive and therefore specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The method steps, processes, and operations described herein are not to be construed as necessarily requiring their performance in the particular order discussed or illustrated, unless specifically identified as an order of performance. It is also to be understood that additional or alternative steps may be employed.

When an element or layer is referred to as being “on,” “engaged to,” “connected to,” or “coupled to” another element or layer, it may be directly on, engaged, connected or coupled to the other element or layer, or intervening elements or layers may be present. In contrast, when an element is referred to as being “directly on,” “directly engaged to,” “directly connected to,” or “directly coupled to” another element or layer, there may be no intervening elements or layers present. Other words used to describe the relationship between elements should be interpreted in a like fashion (e.g., “between” versus “directly between,” “adjacent” versus “directly adjacent,” etc.). As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items.

Although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms may be only used to distinguish one element, component, region, layer or section from another region, layer or section. Terms such as “first,” “second,” and other numerical terms when used herein do not imply a sequence or order unless clearly indicated by the context. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the example embodiments.

Spatially relative terms, such as “inner,” “outer,” “beneath,” “below,” “lower,” “above,” “upper,” and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. Spatially relative terms may be intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” the other elements or features. Thus, the example term “below” can encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.

The term “conduit”, as used herein, is intended to cover all references to pipe as may be normally used in conveying liquid, and/or liquid-like emissions and gaseous and/or gaseous-like emissions. No preference is given or implied concerning the actual method of conveyance of emissions regardless of the type of emissions. The term “ambient temperature” as used herein refers to the temperature of the surrounding environment (e.g., standard temperature and pressure “STP”). Additionally, it should be understood that the terms “contaminate(s)” and “contaminant(s)” are used interchangeably in the present disclosure.

In accordance with one aspect of the subject disclosure, an apparatus for removing contaminants from emissions is disclosed. The apparatus includes a housing that is shaped as a reverse venturi. The housing includes an entry portion for receiving the emissions at a pre-determined entry flow rate, an exit portion for expelling the emissions at a pre-determined exit flow rate, and an enlarged portion disposed between the entry portion and the exit portion of the housing for trapping the contaminants in the emissions. The entry portion, the exit portion, and the enlarged portion of the housing are arranged in fluid communication with each other. In addition, the entry portion of the housing has an entry portion cross-sectional area, the exit portion of said housing has an exit portion cross-sectional area, and the enlarged portion of the housing has an enlarged portion cross-sectional area. In accordance with the reverse venturi shape of the housing, the enlarged portion cross-sectional area is larger than the entry portion cross-sectional area and the exit portion cross-sectional area. Due to this geometry of the housing, the emissions entering the enlarged portion of the housing slow down and pass through the enlarged portion of the housing at a slower velocity relative to a velocity of the emissions passing through the entry portion and the exit portion of the housing. Because the flow of the emissions slows down in the enlarged portion of the housing, a dwell time of the emissions in the enlarged portion of the housing is increased.

The apparatus also includes a mass of reactive material including one or more sorbents that are disposed within the enlarged portion of the housing. The mass of reactive material has a reactive outer surface that is disposed in contact with the emissions. Furthermore, the mass of reactive material contains an amalgam forming metal at the reactive outer surface. The amalgam forming metal in the mass of reactive material chemically binds at least some of the contaminants in the emissions that are passing through the enlarged portion of the housing to the reactive outer surface of the mass of reactive material. One or more sorbent recycling subsystems are disposed in fluid communication with the housing. Each sorbent recycling subsystem receives sorbent from the housing via a sorbent discharge port and returns clean sorbent to the housing via a sorbent return port. The sorbent recycling subsystem(s) include a chemical reagent for separating contaminants from the sorbent in a cleaning and rejuvenation process before the cleaned sorbent is returned to the housing of the fluidized bed apparatus.

In accordance with another aspect of the subject disclosure, an emissions control method is disclosed for removing contaminants from emissions. The method includes the steps of: routing the emissions into a treatment system including a reverse venturi shaped fluidized bed apparatus containing one or more sorbents that chemically binds with contaminants carried in the emissions, and routing the emissions away from the reverse venturi shaped fluidized bed apparatus. In accordance with this method, the sorbent(s) is/are selected from a group of materials including: copper, zinc, tin, sulfur (CZTS) sorbents, copper, zinc, tin, sulfur (CZTS) alloy sorbents, and copper, zinc, tin, sulfur (CZTS) mixture sorbents. The method further includes the step of routing the sorbent(s) through one or more sorbent recycling subsystems for chemical cleaning and rejuvenation.

It is important to maintain optimum process conditions of the sorbents being used to remove contaminated emissions from the reverse venturi shaped fluidized bed apparatus. Therefore, the sorbent is routed from the reverse venturi shaped fluidized bed apparatus and into a sorbent recycling subsystem. The sorbent recycling subsystem is designed to clean and/or rejuvenate the sorbent to optimum conditions before returning the sorbent back into the reverse venturi shaped fluidized bed apparatus. The sorbent recycling subsystem is also designed to separate, and route for disposal, spent and exhausted sorbent from the rest of the sorbent that can be cleaned and/or rejuvenated. The sorbent recycling subsystem is further designed to separate captured contaminates from the sorbent for recycled use in various industries or for proper disposal if there is not a viable recycling option. The sorbent recycling subsystem is further designed to supplement and/or replace sorbent that has been separated for disposal and/or sorbent that has been consumed during the normal operation of removing contaminants from contaminated emissions.

In accordance with another aspect of the subject disclosure, the sorbent recycling subsystem includes one or more monitoring sensors that provide continuous in-line testing and monitoring feedback to maintain constant and consistent optimum sorbent conditions. One exemplary embodiment of the subject disclosure provides at least three separate locations in which three separate sorbent recycling subsystems are installed and configured. A first sorbent recycling subsystem location is provided for CZTS sorbents. A second sorbent recycling subsystem location is provided for CZTS-Alloy sorbents. A third sorbent recycling subsystem location is provided for CZTS-Mixture sorbents. Specific emissions requirements may dictate which sorbent recycling subsystem is specifically required. Depending on the levels of contamination in the reverse venturi fluidized bed apparatus, the reverse venturi fluidized bed apparatus can be configured to use all three of the sorbent recycling subsystems, use none of the sorbent recycling subsystems, or multiple installations of the same sorbent recycling subsystem may be arranged at multiple locations along the reverse venturi fluidized bed apparatus and used simultaneously.

In addition to the advantage of significant savings, the subject apparatus and method are more effective at removing hazardous contaminants from gaseous and non-gaseous emissions compared to known emissions control systems and methods. It is estimated that these improvements are significant enough to enable industries to meet and/or exceed the projected regulation requirements, which is not economically viable with current technology. Therefore, the subject apparatus and methods have the potential of allowing the continued use of fly ash, even if regulatory requirements reclassify fly ash as a hazardous material, thus avoiding significant increased cost to the construction industry, utility power generation industry, and other industries producing non-gaseous ash-type byproducts.

The reverse venturi shaped fluidized bed apparatus may be specifically sized with a certain length to diameter ratio to provide optimum restrictive residence time of the emissions as they pass through the specialized sorbent housed in the device. Through testing and trials, it has been determined that an optimum length to diameter ratio for the housing of the fluidized bed apparatus is between 2.9.1 and 9.8:1 with an exemplary preference of 4.4:1. Therefore, in one exemplary preferred embodiment the diameter is 4.5 feet with a length of 19.8 feet in length, which gives a length to diameter ratio of 4.4:1.

Another feature of the exemplary reverse venturi shaped fluidized bed device is to have predominately rounded outwardly projecting convex ends when viewed from either end outside the vessel. Testing of exemplary examples of the system with a fluidized bed apparatus constructed in this fashion have demonstrated that residence time (the time in which the emissions are in contact with the sorbent) is maximized because the flow of the emissions is randomly turned back on itself with minimized cavitation turbulence, therefore increasing maximized intimate contact. The predominately rounded outwardly projecting convex ends provide a relatively smooth return flow at both ends of the fluidized bed apparatus with minimal cavitation turbulence of the emissions. Turbulent flow with cavitation through a filter is known to impede and/or disrupt flow. Extended residence time in and through the fluidized bed apparatus is desired for optimized contaminate capture and removal from the emissions: however, extended residence time is not optimized if the flow is turbulent flow with cavitation. Various baffles and/or other application specific flow restriction obstacles can be incorporated into the housing of the fluidized bed apparatus.

In accordance with another aspect of the subject disclosure, an exemplary contaminate removal system is provided with reconfigurable segmental components. Each system component can be isolated, bypassed, incorporated, and/or reconfigured for application specific requirements.

According to another aspect of the subject disclosure, the emissions control system contains a mass of reactive sorbent including a copper, zinc, tin, sulfur (CZTS) sorbent, a CZTS-Alloy, and/or a copper, zinc, tin, sulfur (CZTS) mixture sorbent in the fluidized bed apparatus. The fluidized bed apparatus also has additional ports to clean and/or replace sorbent material. The multiple sorbent recycling subsystems disclosed herein provide a method of use for CZTS sorbents, CZTS-Alloy sorbents, and/or CZTS-Mixture sorbents. The exemplary emissions control system may further include one or more pre-filters and/or post-filters that contain a mass of reactive sorbent. The pre-filters and post-filters may be plumbed in parallel or series with the fluidized bed apparatus, depending upon applications specific requirements.

Emissions contaminates from industrial applications include: Hg (Mercury), As (Arsenic), Ba (Barium), Cd (Cadmium), Cr (Chromium), Cu (Copper), Pb (Lead), Sn (Tin), P (Phosphorous), NO₂ (Nitrogen Dioxide), NO₃ (Nitrate), NH₃ (Ammonia). The long list of contaminates precludes the ability to have a one-size-fits-all emissions control solution. Furthermore, emissions control solutions which may work for one contaminate in a gaseous emission might not be effective for the same contaminate in a non-gaseous emission, and vice versa.

International standards and regulations, Federal standards and regulations, State standards and regulations, as well as local standards and regulations all set various levels for allowable parts per million (PPM) of each contaminate in gaseous and/or non-gaseous emissions. Many of these standards and regulations set different allowable levels for contaminates depending upon whether the contaminate is resident in a gaseous emission compared to a non-gaseous emission.

Testing contaminated emissions can be spot checked and/or using continuous in-line monitoring equipment to determine types and levels of contaminates resident in the emissions. Based upon the testing results, specific pre-filters and/or post-filters can be selected for routing contaminated emissions. Each of the pre-filters and/or post-filters contain a specific mass of reactive sorbent as a broad-spectrum of treatment options targeting a specific contaminate resident in the emissions.

The types and/or levels of contaminates resident in emissions changes and/or fluctuates during emissions discharge. Frequent monitoring of contaminates and/or continuous in-line monitoring provides capability to adjust selections of specific pre-filters and/or post-filters to best correspond with the specific contaminates resident in the emissions at any given time during discharge flow.

The present disclosure provides a broad-spectrum matrix, which matches specific types of contaminates resident in gaseous and non-gaseous emissions with a specific reactive sorbent that is effective in the capture and removal of the corresponding contaminate. The matrix also matches the ability for a specific reactive sorbent to be separated from specific captured contaminates so that the contaminate can be either recycled or disposed, as well as whether the sorbent can be rejuvenated and re-used in the emissions control system.

In addition to permanently installed systems for application specific use, the subject system can be configured as a transportable system. Transportable system examples include, but are not limited to, truck mounted systems, barge mounted systems, trailer mounted systems, and rail-car systems. Transportable system applications are useful for providing a bypass to site-built systems by providing a temporary bypass for emissions so that permanent site-built system can be serviced, inspected, and/or repaired. Transportable systems are also useful to provide excess filter capabilities to permanent site-built installations during times when contaminated emissions flow rates exceed the capacity of the permanent site-built system.

There are also a number of advantages attendant to the specialized sorbent described herein in connection with the disclosed apparatus and methods. Generally, the sorbent improves the capabilities of the disclosed emissions equipment to better capture, contain, and/or recycle mercury and other hazardous materials with an efficiency not previously possible using known emission control systems and methods. Another significant benefit of the sorbent disclosed herein is that the sorbent can be used to treat both gaseous and non-gaseous emissions, thus overcoming many of the shortcomings of known methods for treating contaminated non-gaseous emissions, including the secondary emissions generated from primary emissions control processes that are used to treat gaseous emissions. In addition, the sorbent described herein provides improved capabilities to treat gaseous emissions effectively enough to prevent the need for the secondary treatment of non-gaseous emissions that are produced as a by-product of the primary gaseous emissions treatment process. The sorbent disclosed herein is also beneficial because it is reusable. Through a rejuvenation process, the hazardous contaminants that chemically bind with the amalgam forming metal in the sorbent can be harvested away (i.e. removed) from the sorbent, thus restoring the capacity of the sorbent to remove contaminants from the gaseous and/or non-gaseous emissions.

Referring to FIG. 1, a schematic diagram of a typical coal burning power plant 100 is shown. The coal burning power plant 100 includes an industrial facility fluid bed reactor 1 that burns one or more types of coal fuel 2 to produce electrical power 7. The electrical power 7 may then be distributed through power lines 8 to an electrical grid. Combustion within the fluid bed reactor 1 is driven by air 3, flame 4, and the coal fuel 2. The combustion process is used to heat water and produce steam 5. The steam is then used for turning a generator 6, which produces the electrical power 7. Gaseous emissions 10 from the combustion process are released into the environment through stack 9. When the coal burning power plant 100 is not equipped with any emissions control systems (FIG. 1), the emissions 10 include many hazardous contaminants such as fly ash, mercury (Hg), metallic vapors, sulfur dioxide (SO₂), hydrogen chloride (HCl), and other noxious fumes.

Referring to FIG. 2, a schematic of an updated coal burning power plant 200 is shown, which includes a typical emissions control system 202. The emission control system 202 helps to capture and collect some of the hazardous contaminants in the gaseous emissions 10. The emissions control system 202 conveys the gaseous emissions 10 from a fluid bed reactor 1 where combustion occurs into a wet or dry scrubber 11 that removes some of the sulfur dioxide and fly ash contaminants from the gaseous emissions 10. Alternatively or in addition to the conveying the gaseous emissions 10 to the wet or dry scrubber 11, the emissions control system 202 may convey the gaseous emissions 10 into a spray dryer 12 where some sulfur dioxide, noxious fumes, and other contaminants are captured and collected. The emissions may also be routed through a fabric filter unit 13 (i.e. a bag house), which uses filter bags to remove particulates from the flow of gaseous emissions 10. This system collects and removes many contaminants from the gaseous emissions 10 before the gaseous emissions 10 are released into the surrounding atmosphere (i.e. the environment) through the stack 9. The problem with the typical emissions control system 202 illustrated in FIG. 2 is that the nano-sized contaminants, such as mercury, which is contained in metallic vapor emissions, easily passes through the wet or dry scrubber 11, spray dryer 12, and the fabric filter unit 13 of the emissions control system 202.

With reference to FIG. 3, a schematic of a modified coal burning power plant 300 is shown, which includes a sorbent injector 14 and a reverse venturi apparatus 15 in addition to the emissions control system 202 shown in FIG. 2. The sorbent injector 14 operates to add a sorbent into the gaseous emissions 10 and may optionally be disposed upstream of the reverse venturi apparatus 15. More particularly, in the example shown in FIG. 3, the sorbent injector is positioned between the spray dryer 12 and the fabric filter unit 13. Although alternative locations for the reverse venturi apparatus 15 are possible, in FIG. 3, the reverse venturi apparatus is positioned between the fabric filter unit 13 and the stack 9. One primary advantage of this location is that an existing facility would be able to install the reverse venturi apparatus 15 and simply apply for a “Modification to Existing Permit”, saving both time and money compared to applying for a new permit for an entirely new emissions control system. In operation, the gaseous emissions 10 are routed from the fabric filter unit 13 and to the reverse venturi apparatus 15. As will be explained in greater detail below, the reverse venturi apparatus 15 is constructed with internal features that are suitable for collecting and capturing significant amounts of mercury, heavy metals, nano-sized particles, and other contaminants. Therefore, the resulting gaseous emissions 10 exiting the stack 9 are virtually stripped clean of all hazardous contaminants.

With reference to FIGS. 4A-D, the reverse venturi apparatus 15 includes a housing 16 that is shaped as a reverse venturi. It should be appreciated that a venturi may generally be described as a conduit that first narrows from a larger cross-section down to a smaller cross-section and then expands from the smaller cross-section back to a larger cross-section. Therefore, the term “reverse venturi”, as used herein, describes the opposite—a conduit that first expands from a smaller cross-section to a larger cross-section and then narrows back down from the larger cross-section to a smaller cross-section. Specifically, the housing 16 of the disclosed reverse venturi apparatus 15 extends along a central axis 17 and has an entry portion 18, an enlarged portion 19, and an exit portion 20. The entry portion 18 of the housing 16 is sized to receive the gaseous emissions 10 at a pre-determined entry flow rate, which is characterized by an entry velocity V₁ and pressure P₁. The exit portion 20 of the housing 16 is sized to expel the gaseous emissions 10 at a pre-determined exit flow rate, which is characterized by an exit V₃ and pressure P₃. The enlarged portion 19 is disposed between the entry portion 18 and the exit portion 20 of the housing 16 and defines an enlarged chamber 21 therein for trapping the contaminants in the gaseous emissions 10. The enlarged portion 19 of the housing 16 has an interior surface 68 that generally faces the central axis 17. The entry portion 18, the enlarged portion 19, and the exit portion 20 of the housing 16 are arranged sequentially along the central axis 17 such that the entry portion 18, the enlarged portion 19, and the exit portion 20 of the housing 16 are in fluid communication with each other. In other words, the entry portion 18, the enlarged portion 19, and the exit portion 20 of the housing 16 cooperate to form a conduit extending along the central axis 17.

The entry portion 18 of the housing 16 has an entry portion cross-sectional area A₁ that is transverse to the central axis 17 and the exit portion 20 of the housing 16 has an exit portion cross-sectional area A₃ that is transverse to the central axis 17. The entry portion cross-sectional area A₁ may equal (i.e. may be the same as) the exit portion cross-sectional area A₃ such that the pre-determined entry flow rate equals (i.e. is the same as) the pre-determined exit portion flow rate. Alternatively, the entry portion cross-sectional area A₁ may be different (i.e. may be larger or smaller) than the exit portion cross-section area A₃ such that the pre-determined entry flow rate is different (i.e. is less than or is greater than) the pre-determined exit flow rate. It should be appreciated that the term “flow rate”, as used herein, refers to a volumetric flow rate of the emissions.

The enlarged portion 19 of the housing 16 has an enlarged portion cross-sectional area A₂ that is transverse to the central axis 17 and that is larger than the entry portion cross-sectional area A₁ and the exit portion cross-sectional area A₃. Accordingly, the enlarged portion 19 is sized such that a flow velocity V₂ of the gaseous emissions 10 within the enlarged portion 19 of the housing 16 is less than the flow velocity V₁ of the gaseous emissions 10 in the entry portion 18 of the housing 16 and is less than the flow velocity V₃ of the gaseous emissions 10 in the exit portion 20 of the housing 16. This decreased flow velocity in turn increases a dwell time of the gaseous emissions 10 within the enlarged portion 19 of the housing 16. It should be appreciated that the term “dwell time”, as used herein, refers to the average amount of time required for a molecule in the gaseous emissions 10 to travel through the enlarged portion 19 of the housing 16. In other words, the “dwell time” of the enlarged portion 19 of the housing 16 equals the amount of time it takes for all of the emissions in the enlarged chamber 21 to be renewed. It should also be appreciated that the term “cross-sectional area”, as used herein, refers to the internal cross-sectional area (i.e. the space inside the housing 16), which remains the same irrespective of changes to a thickness of the housing 16. Therefore, the enlarged portion cross-sectional area A₂ reflects the size of the enlarged chamber 21 and is bounded by the interior surface 68.

Due to the geometry of the housing 16, the internal pressure P₁ of the gaseous emissions 10 passing through the entry portion 18 of the housing 16 and the internal pressure P₃ of the gaseous emissions 10 passing through the exit portion 20 of the housing 16 are greater than an internal pressure P₂ of the gaseous emissions 10 passing through the enlarged portion 19 of the housing 16. This pressure differential in combination with the fact that the flow velocity V₂ of the gaseous emissions 10 within the enlarged portion 19 of the housing 16 is less than the flow velocity V₁ of the gaseous emissions 10 in the entry portion 18 of the housing 16 and is less than the flow velocity V₃ of the gaseous emissions 10 in the exit portion 20 of the housing 16 causes the gaseous emissions 10 to dwell in the enlarged portion 19 of the housing 16. As a result of the pressure and velocity differentials noted above and because the gaseous emissions 10 will naturally expand to occupy the entire volume of the enlarged chamber 21, an expansion force is thus imparted on the gaseous emissions 10 in the enlarged portion 19 of the housing 16. This in combination with the effects of laminar flow, pneumatic dynamics, and gas behavior physics, the resultant increase in dwell time improves the ability of the reverse venturi apparatus 15 to efficiently capture and thereby remove contaminants from the gaseous emissions 10.

The housing 16 may have a variety of different shapes and configurations. For example and without limitation, the entry portion 18, the enlarged portion 19, and the exit portion 20 of the housing 16 illustrated in FIGS. 4A-D all have circular shaped cross-sectional areas A₁, A₂, A₃. Alternatively, the cross-sectional areas A₁, A₂, A₃ of one or more of the entry portion 18, the enlarged portion 19, and the exit portion 20 of the housing 16 may have a non-circular shape, where various combinations of circular and non-circular shaped cross-sectional areas are possible and are considered to be within the scope of the subject disclosure. In some configurations, the enlarged portion 19 of the housing 16 may have a divergent end 22 and a convergent end 23. In accordance with these configurations, the enlarged portion 19 of the housing 16 gradually tapers outwardly from the entry portion cross-sectional area A₁ to the enlarged portion cross-sectional area A₂ at the divergent end 22. In other words, the cross-section of the enlarged portion 19 of the housing 16 increases at the divergent end 22 moving in a direction away from the entry portion 18 of the housing 16. By contrast, the enlarged portion 19 of the housing 16 gradually tapers inwardly from the enlarged portion cross-sectional area A₂ to the exit portion cross-sectional area A₃ at the convergent end 23. In other words, the cross-section of the enlarged portion 19 of the housing 16 decreases at the convergent end 23 moving in a direction towards the exit portion 20 of the housing 16. Therefore, it should be appreciated that the gaseous emissions 10 in the enlarged portion 19 of the housing 16 generally flow from the divergent end 22 to the convergent end 23. In embodiments where the entry portion 18, the enlarged portion 19, and the exit portion 20 of the housing 16 all have circular shaped cross-sectional areas A₁, A₂, A₃, the divergent and convergent ends 22, 23 of the housing 16 may generally have a conical shape. Notwithstanding, alternative shapes for the divergent and convergent ends 22, 23 of the enlarged portion 19 of the housing 16 are possible. By way of example and without limitation, the divergent and convergent ends 22, 23 may have a polygonal shape for improved manufacture ease while avoiding any significant detrimental effects to the flow of the gaseous emissions 10 through the housing 16 of the reverse venturi apparatus 15. In another alternative configuration, the enlarged portion 19 of the housing 16 may have a shape resembling a sausage with relatively abrupt transitions between the entry portion 18 and the divergent end 22 and the convergent end 23 and the exit portion 20. It is presumed that a smooth transition is preferred to an abrupt transition because laminar flow behavior of the gaseous emissions 10 may be preferred. However, minor disturbances to the laminar flow of the gaseous emissions 10 at abrupt transitions are not perceived to be an overwhelming penalty, but rather may provide enhanced flow in areas where increased dwell time is not necessary.

With continued reference to FIGS. 4A-D and with additional reference to FIGS. 5-11, a mass of reactive material 24 is disposed within the enlarged portion 19 of the housing 16. The mass of reactive material 24 has a reactive outer surface 25 that is disposed in contact with the gaseous emissions 10. In addition, the mass of reactive material 24 contains an amalgam forming metal at the reactive outer surface 25 that chemically binds at least some of the contaminants in the gaseous emissions 10 that are passing through the enlarged portion 19 of the housing 16 to the reactive outer surface 25 of the mass of reactive material 24. In this way, the contaminants bound to the reactive outer surface 25 of the mass of reactive material 24 remain trapped in the enlarged portion 19 of the housing 16 and are thus removed from the flow of the gaseous emissions 10 exiting the enlarged portion 19 of the housing 16 and entering the exit portion 20 of the housing 16. It should be appreciated that the term “amalgam forming metal”, as used herein, describes a material, selected from a group of metals, that is capable of forming a compound with one or more of the contaminants in the gaseous emissions 10. By way of non-limiting example, the amalgam forming metal may be zinc and the contaminant in the gaseous emissions 10 may be mercury such that an amalgam of zinc and mercury is formed when the gaseous emissions 10 come into contact with the reactive outer surface 25 of the mass of reactive material 24.

It should be appreciated that the enlarged portion 19 of the housing 16 must be sized to accommodate the pre-determined entry flow rate of the gaseous emissions 10 while providing a long enough dwell time to enable the amalgam forming metal in the mass of reactive material 24 to chemically bind with the contaminants in the gaseous emissions 10. Accordingly, to achieve this balance, the enlarged portion cross-sectional area A₂ may range from 3 square feet to 330 square feet in order to achieve a dwell time ranging from 1 second to 2.5 seconds. The specified dwell time is necessary to allow sufficient time for the contaminants in the gaseous emissions 10 to chemically bind to the amalgam forming metal in the mass of reactive material 24. Thus, the range for the enlarged portion cross-sectional area A₂ was calculated to achieve this residence time for coal burning power plants 100 with outputs ranging from 1 Mega Watt (MW) to 6,000 Mega Watts (MW). As is known in the chemical arts, the amalgam forming metal may be a variety of different materials. By way of non-limiting example, the amalgam forming metal may be selected from a group consisting of zinc, iron, and aluminum. It should also be appreciated that the housing 16 is made from a material that is different from the mass of reactive material 24. By way of non-limiting example, the housing 16 may be made from steel, plastic, or fiberglass.

The mass of reactive material 24 may be provided in a variety of different, non-limiting configurations. With reference to FIG. 4A, the mass of reactive material 24 is shown coating the interior surface 68 of the housing 16. Alternatively, with reference to FIGS. 5-11, the mass of reactive material 24 may form one or more obstruction elements 26 a-j that are disposed within the enlarged portion 19 of the housing 16. As such, the obstruction element(s) 26 a-j create a tortuous flow path 27 for the gaseous emissions 10 passing through the enlarged portion 19 of the housing 16. Accordingly, the obstruction element(s) 26 a-j increase the dwell time for the gaseous emissions 10 passing through the enlarged portion 19 of the housing 16. Several of the embodiments discussed below break up the flow of the gaseous emissions 10 passing through the enlarged portion 19 of the housing 16 so completely that the tortuous flow path 27 created is completely random, which greatly enhances the opportunity for chemical reactions between the contaminants in the gaseous emissions 10 and the amalgam forming metal in the mass of reactive material 24.

The obstruction element(s) 26 a-j in each of the configurations shown in FIGS. 5-11 present a large surface area, such that the reactive outer surface 25 of the mass of reactive material 24 is large. This is advantageous because chemical reactions between the amalgam forming metal in the reactive outer surface 25 of the mass of reactive material 24 and contaminants in the gaseous emissions 10 allow the enlarged portion 19 of the housing 16 to trap, capture, and/or collect the contaminants, thereby removing/eliminating them from the gaseous emissions 10. Accordingly, the amount of contaminants that the enlarged portion 19 of the housing 16 can remove from the gaseous emissions 10 passing through the enlarged chamber 21 is proportional to the size of the reactive outer surface 25 of the mass of reactive material 24 in the enlarged portion 19 of the housing 16. In addition, the complex surface shapes and/or texture of the obstruction(s) 26 a-j can provide additional surface area to facilitate the physical capture of contaminants whether the capture is the result of a chemical reaction between the contaminants and the amalgam forming metal or not.

Referring again to FIG. 3, the sorbent that is added to the emissions by the sorbent injector 14 contains the amalgam forming metal. As such, the amalgam forming metal in the sorbent chemically binds with at least some of the contaminants in the gaseous emissions 10 before the gaseous emissions 10 enter the enlarged portion 19 of the housing 16. Although the sorbent may have a number of different compositions, the sorbent may be, for example, a zinc (Zn) powder or a copper, zinc, tin, sulfur (CZTS) compound. Because the sorbent chemically binds with at least some of the contaminants in the gaseous emissions 10 before the gaseous emissions 10 enter the enlarged portion 19 of the housing 16, the sorbent helps the mass of reactive material 24 remove the contaminants from the gaseous emissions 10.

With reference to FIG. 5, the obstruction elements 26 a-j are provided in the form of a series of staggered baffles 26 a that extend from the interior surface 68 of the enlarged portion 19 of the housing 16. The series of staggered baffles 26 a are transverse to the central axis 17 and give the tortuous flow path 27 a serpentine shape. The serpentine shape of the tortuous flow path 27 increases the dwell time of the gaseous emissions 10 in the enlarged portion 19 of the housing 16, which in turn improves the capture and removal of the contaminants in the gaseous emissions 10 by the mass of reactive material 24 forming the series of staggered baffles 26 a. In one variation, the series of staggered baffles 26 a are made of zinc. In another variation, the series of staggered baffles 26 a are made of a non-zinc material that is zinc coated. It should be appreciated that the placement of the staggered baffles 26 a need not be equally or symmetrically oriented along a length of the central axis 17 because some applications may benefit from larger spaces between adjacent baffles 26 a while other applications may benefit from smaller spaces between adjacent baffles 26 a. It should also be appreciated that the series of staggered baffles 26 a can be replaced and/or cleaned as necessary if they become saturated during operation of the reverse venturi apparatus 15.

With reference to FIGS. 6A-B, the at least one obstruction element 26 a-j is alternatively in the form of an auger-shaped baffle 26 b. The auger-shaped baffle 26 b extends helically within the enlarged portion 19 of the housing 16 along and about the central axis 17. Accordingly, the auger-shaped baffle 26 b gives the tortuous flow path 27 a spiraling shape. The spiraling shape of the tortuous flow path 27 increases the dwell time of the gaseous emissions 10 in the enlarged portion 19 of the housing 16, which in turn improves the capture and removal of the contaminants from the gaseous emissions 10 by the mass of reactive material 24 forming the auger-shaped baffle 26 b. In one variation, the auger-shaped baffle 26 b is made of zinc. In another variation, the auger-shaped baffle 26 b is made of a non-zinc material that is zinc coated. In yet another variation, the auger-shaped baffle 26 b is mechanically driven such the auger-shaped baffle 26 b rotates within the enlarged portion 19 of the housing 16 about the central axis 17. Rotation of the auger-shaped baffle 26 b can either artificially accelerate or artificially slow the flow of the gaseous emissions 10 through the enlarged portion 19 of the housing 16, depending upon which direction the auger-shaped baffle rotates. It should be appreciated that the auger-shaped baffle 26 b can be replaced and/or cleaned as necessary if the auger-shaped baffle 26 b becomes saturated during operation of the reverse venturi apparatus 15.

With reference to FIGS. 7A-B, the at least one obstruction element 26 a-j is a plurality of baffles 26 c. Each baffle 26 c extends transversely across the enlarged portion 19 of the housing 16 from the interior surface 68 of the enlarged portion 19 of the housing 16. The baffles 26 c are spaced apart from one another along the central axis 17 and each baffle 26 c includes orifices 28 that permit the flow of the gaseous emissions 10 through the baffles 26 c. Of course it should be appreciated that any number of baffles 26 c are possible, including a configuration containing only a single baffle 26 c. It should also be appreciated that the size, shape, and number of orifices 28 in each baffle 26 c may vary. For example, the baffles 26 c may be provided in the form of a screen, where the orifices 28 are formed between the crossing wires of the screen. The orifices 28 in the baffles 26 c restrict the flow of the gaseous emissions 10 in the enlarged portion 19 of the housing 16 and thus increase the dwell time of the gaseous emissions 10 in the enlarged portion 19 of the housing 16. This improves the capture and removal of the contaminants from the gaseous emissions 10 by the mass of reactive material 24 forming the baffles 26 c. In one variation, the baffles 26 c are made of zinc. Another variation, the baffles 26 c are made of a non-zinc material that is zinc coated. It should be appreciated that the baffles 26 c can be replaced and/or cleaned as necessary if they become saturated during operation of the reverse venturi apparatus 15. In yet another variation, the size(s) of the orifices 28 in one of the baffles 26 c is different than the size(s) of the orifices 28 in an adjacent one of the baffles 26 c. By using different sizes of orifices 28 in different baffles 26 c, the flow of gaseous emissions 10 can be accelerated and/or restricted to improve the capture and removal of the contaminants in the gaseous emissions 10 by the mass of reactive material in the baffles 26 c. In a similar way, the baffles 26 c need not be equally spaced apart in the enlarged chamber 21, nor do the orifices 28 in one of the baffles 26 c need to be the same size, shape, or in the same location as the orifices 28 in an adjacent baffle 26 c. By taking advantage of different sizes, shapes, and locations of the orifices 28 from one of the baffles 26 c to another and by taking advantage of different spacing of the baffles 26 c, the dwell time of the gaseous emissions 10 in the enlarged portion 19 of the housing 16 can be increased so as to promote increased contact with the physical and chemical capture and collection sites along the mass of reactive material 24.

In other alternative configurations shown in FIGS. 8-11, the at least one obstruction element 26 a-j may not be fixed to the housing 16 itself, but instead may be freely positioned inside the enlarged portion 19 of the housing 16. In such configurations, the at least one obstruction element 26 a-j may include various forms of obstruction media 26 d-j. Like obstruction elements 26 a-c, the obstruction media 26 d-j is capable of being made from zinc or from a non-zinc material that is zinc coated. Zinc is easily melted allowing complex shapes to be cast using normal molding methods, lost wax investment processes, centrifugal processes, and the like. Other construction methods will readily include machining, extrusion, sintering, stamping, hot forging and forming, laser cutting, and the like. Alternatively, steel may be used to create an underlying shape, which is then subsequently coated or plated in zinc as a surface cover. The obstruction media 26 d-j can be used to completely fill the entire enlarged chamber 21, partially fill the enlarged chamber 21, or fill in between the baffles 26 c previously described in connection with FIGS. 7A-B.

FIG. 8 illustrates a configuration where the at least one obstruction element 26 a-j is a plurality of fragments 26 d that are contained in the enlarged portion 19 of the housing 16. In accordance with this configuration, the gaseous emissions 10 pass through the spaces between adjacent fragments 26 d as the gaseous emissions 10 travel through the enlarged portion 19 of the housing 16 from the entry portion 18 to the exit portion 20 of the housing 16. To this end, the plurality of fragments 26 d may be provided with an irregular shape such that the fragments 26 d loosely pack with each other in the enlarged portion 19 of the housing 16. In one non-limiting example, the plurality of fragments 26 d may be made of mossy zinc. Mossy zinc is popcorn shaped zinc construction that is produced by dipping molten zinc into a cooling liquid such as water. The resulting drip of molten zinc solidifies into a relatively small spheroidal structure with extremely high surface area to volume ratios. In addition, the surface area of the resultant structure has a moss-like surface texture. These structures can be produced in a range of sizes for application specific uses. Some steel processes can produce steel versions of complex spheroidal structures similar to mossy zinc, which may be zinc coated.

The loose pack nature of the plurality of fragments 26 d in FIG. 8 gives the tortuous flow path 27 a random shape, which increases the dwell time of the gaseous emissions 10 in the enlarged portion 19 of the housing 16. This in turn improves the capture and removal of the contaminants from the gaseous emissions 10 by the mass of reactive material 24 forming the plurality of fragments 26 d. The plurality of fragments 26 d in FIG. 8 can be replaced and/or cleaned as necessary if they become saturated during the operation of the reverse venturi apparatus 15.

In another alternative configuration shown in FIG. 9, the at least one obstruction element 26 a-j is a plurality of entangled strands 26 e that are disposed in the enlarged portion 19 of the housing 16. The plurality of entangled strands 26 e thus form a wool-like material in the enlarged portion 19 of the housing 16. In accordance with one possible configuration, the plurality of entangled strands 26 e are folded and crumpled like steel wool to form a mass with a very large surface area. The entangled strands 26 e themselves may be of the same composition, thickness, and length or alternatively may be a mixture of different compositions, thicknesses, and/or lengths. In one variation, the plurality of entangled strands 26 e are made from zinc wire and are randomly entangled to form a zinc wool. The zinc wool can be produced with varying levels of density and/or sizes of wire so as to provide specific flow restriction capabilities. In another variation, the plurality of entangled strands 26 e are made from steel wire and are randomly entangled to form a steel wool. The steel wool may be zinc coated. The relatively loose packed nature of the plurality of entangled strands 26 e in FIG. 9 gives the tortuous flow path 27 a random shape, which increases the dwell time of the gaseous emissions 10 passing through the enlarged portion 19 of the housing 16. This in turn improves the capture and removal of the contaminants in the gaseous emissions 10 by the mass of reactive material 24 forming the plurality of entangled strands 26 e. It should be appreciated that the plurality of entangled strands 26 e can be replaced and/or cleaned as necessary if they become saturated during operation of the reverse venturi apparatus 15.

With reference to FIG. 10, another alternative configuration is illustrated where the at least one obstruction element 26 a-j is a filter element 26 f The filter element 26 f extends transversely across the enlarged portion 19 of the housing 16 relative to the central axis 17. The filter element 26 f is porous such that the pores in the filter element 26 f allow the gaseous emissions 10 to pass through the filter element 26 f as the gaseous emissions 10 flow through the enlarged portion 19 of the housing 16 from the entry portion 18 to the exit portion 20 of the housing 16. The arrangement of the filter element 26 f which may be made of a sintered metal, gives the tortuous flow path 27 a random shape, which increases the dwell time of the gaseous emissions 10 passing through the enlarged portion 19 of the housing 16. This in turn improves the capture and removal of the contaminants in the gaseous emissions 10 by the mass of reactive material 24 forming the filter element 26 f. The sintered metal of the filter element 26 f is preferably made of zinc or a non-zinc material that is zinc coated. It should be appreciated that the filter element 26 f can be replaced and/or cleaned as necessary if it becomes saturated during operation of the reverse venturi apparatus 15.

Referring to FIG. 11, the at least one obstruction element 26 a-j is illustrated as a combination of the plurality of baffles 26 c shown in FIGS. 7A-B and a plurality of fragments 26 g-j, which have different sizes and which are similar to the plurality of fragments 26 d shown in FIG. 8. In accordance with this alternative configuration, the plurality of baffles 26 c and the plurality of fragments 26 g-j are disposed in the enlarged portion 19 of the housing 16 Like in FIGS. 7A-B, the plurality of baffles 26 c illustrated in FIG. 11 extend transversely across the enlarged portion 19 of the housing 16 from the interior surface 68 of the enlarged portion 19 of the housing 16. Additionally, the plurality of baffles 26 c are spaced apart relative to one another along the central axis 17 such that the baffles 26 c divide the enlarged chamber 21 into multiple sections. Orifices 28 in each of the baffles 26 c permit the flow of the gaseous emissions 10 through the baffles 26 c. The plurality of fragments 26 g-j are disposed between adjacent baffles 26 c (i.e. are disposed in the multiple sections of the enlarged chamber 21).

As illustrated in FIG. 11 and in FIGS. 12A-D, the plurality of fragments 26 g-j are form the mass of reactive material 24. The plurality of fragments 26 g-j may be provided in different sizes where the plurality of fragments 26 g-j are grouped by similar size (i.e. fragments 26 g, 26 h, 26 i, and 26 j are in separate groups) and are separated from fragments of another size by the baffles 26 c. For example, the groups of fragments 26 g-j may be arranged such that the size of the fragments 26 g-j decreases moving away from the entry portion 18 of the housing 16 and toward the exit portion 20 of the housing 16. In other words, the size of the fragments 26 g-j in the various groups may be graduated and decreasing moving in an overall flow direction of the gaseous emissions 10 in the enlarged portion 19 of the housing 16. In one variation, the fragments 26 g-j are made of zinc. For example, the fragments 26 g-j may be formed by dripping molten zinc into a cooling liquid to create a popcorn-like structure with an exceptionally large surface area and a random, moss-like surface texture. It should be appreciated that in another variation, different sized fragments 26 g-j may be mixed together and therefore are not separated into groups based on size.

As FIGS. 13A-C illustrate, several alternative shaped obstruction elements 26 k-m are shown in the form of a loose material, which may be used in addition to or instead of the plurality of fragments 26 d and 26 g-j shown in FIGS. 8 and 11. FIG. 13A illustrates an example where the obstruction 26 k forms the mass of reactive material 24 and has an asterisk-like shape, which is similar to the shape of the child's toy called “Jacks”. FIG. 13B illustrates another example where the alternative shaped obstruction element 26 k-m is a plurality of crystalline flakes 261 (one shown) that form the mass of reactive material 24 and that may be positioned in the enlarged portion 19 of the housing 16 like the fragments 26 d and 26 g-j shown in FIGS. 8 and 11. The crystalline flakes 261 have a shape that is similar to that of a snowflake. FIG. 13C illustrates yet another example where the alternative shaped obstruction element 26 k-m is a plurality of wire coils 26 m (one shown) that form the mass of reactive material 24 and that may be positioned in the enlarged portion 19 of the housing 16 like the fragments 26 d and 26 g-j shown in FIGS. 8 and 11. It should be appreciated that obstructions 26 k and the plurality of crystalline flakes 261 may be made of zinc or a non-zinc material that is zinc coated using various processes, including without limitation, lost wax forging and 3D printing. The plurality of wire coils 26 m may be made, for example, by wrapping zinc wire around a mandrel core similar to the shape of a spring, except after winding around the mandrel core the entire coil of wrapped wire is slit along the length of the mandrel core so that individual rings of coil are generated. It should also be appreciated that the alternative shaped obstruction elements 26 k-m may or may not completely fill the enlarged chamber 21.

It should be appreciated that the various types of obstruction elements 26 a-k described above can be mixed and matched to create various combinations. Examples of mixing and matching include combining one or more baffles 26 a-c shown in FIGS. 5, 6A-B, and 7A-B with the plurality of fragments 26 d and 26 g-j shown in FIGS. 8 and 11. Other examples of mixing and matching include combining the plurality of entangled strands 26 e shown in FIG. 9 with the plurality of fragments 26 d and 26 g-j shown in FIGS. 8 and 11. Other alternative configurations are possible that combine the various types of obstruction elements 26 a-k described above with other filter materials such as activated carbon. Activated carbon collects contaminants like a sponge and by surface contact. Therefore, limited quantities of activated carbon can be introduced into the enlarged portion 19 of the housing 16 to act in conjunction with the various types of obstruction elements 26 a-k described above. Advantageous, the obstruction elements 26 a-k would hold the activated carbon in the enlarged portion 19 of the housing 16 so that the activated carbon is disposed relatively statically throughout the enlarged chamber 21. This scenario is opposite to typical emission control systems, which release activated carbon into the flow of gaseous emissions 10. Because the activated carbon is not free to flow with the gaseous emissions a more efficient use of activated carbon is possible. Those skilled in the art will readily appreciate that the disclosed variations of the reverse venturi apparatus 15 are merely exemplary and that many combinations well beyond the few examples disclosed herein are possible and desirable to address specific applications.

With reference to FIG. 14, another exemplary reverse venturi apparatus 15′ is illustrated that includes two enlarged portions 19, 19′ that are joined together in series by conduit 38. One enlarged portion 19 of the housing 16 extends between the entry portion 18 of the housing 16 and the conduit 38 while the other enlarged portion 19′ extends between the conduit 38 and the exit portion 20 of the housing 16. Thus, the tortuous flow path 27 for the gaseous emissions 10 is elongated. In accordance with this configuration, the gaseous emissions 10 are routed from enlarged portion 19 through conduit 38 and to enlarged portion 19′ where additional contaminants are collected and/or captured. It should also be appreciated that the subject disclosure is not limited to using just one or two enlarged portions 19, 19′ in series, because some applications with an extensive volume of emissions and/or heavy contamination levels may require numerous enlarged portions connected together in series.

Referring to FIG. 15, another exemplary reverse venturi apparatus 15″ is illustrated that includes two enlarged portions 19, 19″ that are joined together in parallel. A 3-way inlet valve 39 controls the flow of gaseous emissions 10, directing the gaseous emissions 10 into and through either conduit 41 or conduit 42. A 3-way outlet valve 40 directs the gaseous emissions 10 to exit from either conduit 41 or conduit 42 without back-flowing directly from conduit 41 into conduit 42, or vice versa. The gaseous emissions 10 enter enlarged portion 19 through entry portion 18 and exit through exit portion 20 when the gaseous emissions 10 are routed through conduit 41. The gaseous emissions 10 enter enlarged portion 19″ through entry portion 18″ and exit through exit portion 20″ when the gaseous emissions 10 are routed through conduit 42. One benefit of the reverse venturi apparatus 15″ shown in FIG. 15 is that when one of the enlarged portions 19, 19″ requires maintenance, servicing, or cleaning, it can be isolated and taken off-line without shutting down the entire system, because the other one of the enlarged portions 19, 19″ can remains in service.

Over time, the chemical reactions occurring on the reactive outer surface 25 of the mass of reactive material 24 and/or the physical capture of contaminants may lead to a saturation point for the mass of reactive material 24 wherein the efficiency of the reverse venturi apparatus 15 is reduced. The arrangement shown in FIG. 15 therefore allows for the removal, replacement, and/or cleaning of the mass of reactive material 24 in the enlarged portions 19, 19″ of the housing 16 to restore the reverse venturi apparatus to pre-saturation efficiency performance without requiring a complete shutdown.

The process of contaminant removal from the saturated mass of reactive material will specifically depend upon the type of contaminants and the type of amalgam forming metal being used. Access to the enlarged chambers 21, 21″, which are disposed inside the enlarged portions 19, 19″ of the housing 16 will be commensurate with the type of obstruction used. When relatively small loose obstructions are used, a pouring and/or draining type access will be required. If the obstructions are relatively large blocks, plates, baffles, or assemblies, then appropriate lifting and handling methods and access will be required.

Still referring to FIG. 15, the reverse venturi apparatus 15 may include one or more spray nozzles 81 that are disposed in fluid communication with the enlarged portions 19, 19″ of the housing 16. The spray nozzles 81 are positioned to spray a deoxidizing acid over the mass of reactive material 24 in the enlarged portions 19, 19″ of the housing 16. In operation, the deoxidizing acid washes the mass of reactive material 24 of the contaminants in order to rejuvenate the mass of reactive material 24. Optionally, drains 82 may be disposed in fluid communication with the enlarged portions 19, 19″ of the housing 16 to transport the solution of used deoxidizing acid and contaminants away from the enlarged portions 19, 19″ of the housing 16. Advantageously, saturated zinc, whether it is a coating on steel, or a solid zinc structure, can be recycled and reclaimed. Therefore, the material used in the obstructions can be reused and reclaimed. In addition, many of the contaminants which are captured, especially the heavy metals such as mercury, may be able to be reused and reclaimed in lighting and chlorine manufacture.

With reference to FIG. 16, another exemplary reverse venturi apparatus 15 is illustrated where the enlarged chamber 45 has a significantly larger volume compared to the volume of entrance conduit 43 and exiting conduit 44. The enlarged portion 46 can be round, square, triangular, oval, or virtually any one of many shapes as may be desired (where a rectangular shape is shown), in order to achieve an enlarged tortuous flow path 77 for the gaseous emissions flowing through the enlarged portion 46.

With reference to FIG. 17, a block diagram of a typical gaseous emission control system is shown. Gaseous emissions are routed from a furnace 47 to an electrostatic precipitator (ESP) 48, and then to a fluidized gas desulfurization (FGD) unit 49, and then through a fabric filter (FF) unit 50, before being released to atmosphere through a stack 51. A first concentrate 52 of contaminants is removed from the gaseous emissions at the ESP 48. In a similar fashion, a second concentrate 53 of contaminants is removed from the gaseous emissions at the FGD unit 49. The second concentrate 53 produced by the FGD unit 49, which often contains mercury and other heavy metals, is typically diverted into wastewater. A third concentrate 54 of contaminants is removed from the gaseous emissions at the FF unit 50.

With reference to FIGS. 18A-B, the block diagram of FIG. 17 has been modified with introduction point options for sorbent injection and an additional step has been added where the gaseous emissions are passed through the reverse venturi apparatus 15 described above. In FIG. 18A, a first sorbent introduction point 55 is shown positioned between the furnace 47 and the ESP 48. Alternatively, in FIG. 18B, a second sorbent induction point 56 is shown positioned between the FGD unit 49 and the FF unit 50. Which option is deemed to be best for sorbent will be dependent upon the existing configuration and condition of the plant. There are numerous other introduction points and/or combinations of introduction points where the sorbent can be introduced other than the two options depicted in FIGS. 18A-B, therefore these two options are illustrated for demonstrative purposes. The reverse venturi apparatus 15 in FIGS. 18A-B is located after the FF unit 50 and before the stack 51. The reverse venturi apparatus 15 can be constructed in accordance with any of the aforementioned examples described above, as may be appropriate for various applications. In the end, the final gaseous emissions released to atmosphere through the stack 51 after exiting the reverse venturi apparatus 15 will be capable of meeting and exceeding current and future EPA emissions regulations and requirements.

The method illustrated by FIGS. 18A-B includes the steps of burning a fuel in the furnace 47 to generate gaseous emissions that contain contaminants, routing the gaseous emissions from the furnace 47 to the ESP 48, and removing a first portion particulate contaminants in the gaseous emissions using the ESP 48. In accordance with the step of removing a first portion particulate contaminants in the gaseous emissions using the ESP 48, the first concentrate 52 is formed, which contains the first portion of particulate contaminants that have been removed from the gaseous emissions by the ESP 48. It should be understood that in operation, the ESP 48 utilizes an induced electrostatic charge to remove fine contaminant particles from the gaseous emissions. The method also includes the steps of routing the gaseous emissions from the ESP 48 to the FGD unit 49 and removing sulfur dioxide contaminants in the gaseous emissions using the FGD unit 49. In accordance with the step of removing sulfur dioxide contaminants in the gaseous emissions using the FGD unit 49, the second concentrate 53 is formed containing the sulfur dioxide contaminants that have been removed from the gaseous emissions by the FGD unit 49. The method further includes the steps of routing the gaseous emissions from the FGD unit 49 to the FF unit 50 (i.e. a bag house) and removing a second portion of particulate contaminants in the gaseous emissions using the FF unit 50. In accordance with the step of removing a second portion of particulate contaminants in the gaseous emissions using the FF unit 50, the third concentrate 54 is formed containing the second portion of particulate contaminants that have been removed from the gaseous emissions by the FF unit 50. It should be understood that in operation, contaminant particles are removed from the gaseous emissions when the gaseous emissions pass through the one or more fabric filters (not shown) of the FF unit 50.

In accordance with the subject disclosure, the method further includes the steps of routing the gaseous emissions from the FF unit 50 to the reverse venturi apparatus 15 and removing heavy metal contaminants in the gaseous emissions using the reverse venturi apparatus 15. In accordance with the step of removing heavy metal contaminants in the gaseous emissions using the reverse venturi apparatus 15, the gaseous emissions pass by (i.e. flow over) the mass of reactive material disposed in the reverse venturi apparatus 15. The amalgam forming metal in the mass of reactive material chemically binds with the heavy metal contaminants in the gaseous emissions. Accordingly, the mass of reactive material traps the heavy metal contaminants in the reverse venturi apparatus 15 when the heavy metal contaminants bind to the amalgam forming metal in the mass of reactive material. The method may then proceed with routing the gaseous emissions from the reverse venturi apparatus 15 to a stack 51 that vents the gaseous emissions to the surrounding atmosphere. It should also be appreciated that the reverse venturi apparatus 15 advantageously has a relatively small equipment footprint, allowing it to be easily installed as a retrofit in line between the emission control devices 48, 49, 50 of existing systems and the stack 51 to atmosphere.

Optionally, the method may include the step of injecting a sorbent into the gaseous emissions. In accordance with this step and as shown in FIG. 18A, the sorbent may be injected into the gaseous emissions at the first sorbent introduction point 55 that is disposed between the furnace 47 and the ESP 48. Alternatively, as shown in FIG. 18B, the sorbent may be injected into the gaseous emissions at the second sorbent introduction point 56 that is disposed between the FGD unit 49 and the FF unit 50. The sorbent contains the amalgam forming metal such that the sorbent binds with at least some of the heavy metal contaminants in the gaseous emissions before the gaseous emissions enter the reverse venturi apparatus 15. By injecting the sorbent into the gaseous emissions at the first sorbent introduction point 55 or the second sorbent introduction point 56, more mercury, heavy metals, and acid gasses can be collected in the FF unit 50 at levels that were previously impossible to achieve. As noted above, the amalgam forming metal may be selected from a group consisting of zinc, iron, and aluminum and the sorbent may be, for example, a CZTS compound. The sorbent is able to be regenerated and rejuvenated so that the hazardous contaminants can be harvested and recycled.

With reference to FIG. 19, a block diagram of a typical non-gaseous emission control system is shown. Liquid and/or liquid-like emissions can be routed from a fluidized gas desulfurization (FGD) unit 59 and/or routed from a wet scrubber unit 58 into a lime treatment unit 60 before being routed to a settling pond 61. After an appropriate period of time, the non-gaseous emissions will be routed out of the settling ponds 61 into either a process system for dry disposal preparation 64 or to a dewatering system 62. The non-gaseous emissions that are routed through the process for dry disposal 64 are prepared for disposal in a landfill 65. The non-gaseous emissions that are routed through the dewatering system 62, which sometimes may include a recirculation system, are prepared for use in a secondary industrial process 63, which for example, may involve the manufacture of gypsum and/or cement. The non-gaseous emissions that are not routed out the settling ponds 61 into the dewatering systems 62 or into the processes for dry disposal 64 are routed for discharge into waterways 66. The final non-gaseous emissions released into the waterways 66 are not as regulated as they will be in coming years. The proposed EPA water emissions regulations and requirements will be extraordinarily restrictive compared to the emissions allowed into waterways at the present time. The industries with contaminated liquid emissions requiring discharge into waterways have current emissions control technology which has virtually no possibility of meeting and/or complying with the coming EPA regulations.

With reference to FIG. 20, the block diagram of FIG. 19 has been modified with one or more treatment tanks 67, which contain the sorbent described above. The treatment tanks 67 are located after the non-gaseous emissions are routed out of the settling pond 61 and before they are discharged into the waterways 66. The method illustrated by FIG. 20 includes the steps of collecting non-gaseous emissions that contain contaminants, passing the non-gaseous emissions through the FGD unit 59 and/or the wet scrubber 58 to remove some of the contaminants in the non-gaseous emissions, routing the non-gaseous emissions from the FGD unit 59 and/or the wet scrubber 58 to a lime treatment unit 60, and passing the non-gaseous emissions through the lime treatment unit 60 to soften the non-gaseous emissions through Clark's process. It should be understood that in operation, the lime treatment unit 60 removes certain ions (e.g. calcium (Ca) and magnesium (Mg)) from the non-gaseous emissions by precipitation. The method also includes the steps of routing the non-gaseous emissions from the lime treatment unit 60 to the settling pond 61 where some of the contaminants in the non-gaseous emissions are removed by sedimentation, dewatering a first portion of the non-gaseous emissions in the settling pond 61 and using the dewatered by-product in a secondary industrial process 63, and removing a second portion of the non-gaseous emissions from the settling pond 61 and subjecting the second portion of the non-gaseous emissions to a dry disposal process 64. In accordance with the step of dewatering the first portion of the non-gaseous emissions in the settling pond 61 and using the dewatered by-product in the secondary industrial process 63, dewatering process may include recirculation of the first portion of the non-gaseous emissions and the secondary industrial process 63 may involve, for example, the manufacture of gypsum or the manufacture of cement. In accordance with the step of removing the second portion of the non-gaseous emissions from the settling pond 61 and subjecting the second portion of the non-gaseous emissions to the dry disposal process 64, the dry disposal process 64 may include depositing the second portion of the non-gaseous emissions in the landfill 65.

In accordance with the subject disclosure, the method further includes the step of routing a third portion of the non-gaseous emissions in the settling pond 61 to the treatment tanks 67 containing the disclosed sorbent. The sorbent contains an amalgam forming metal that binds with heavy metal contaminants in the third portion of non-gaseous emissions. Accordingly, the sorbent traps the heavy metal contaminants in the treatment tanks 67 when the heavy metal contaminants bind with the sorbent and settle/precipitate out of the non-gaseous emissions. The method may then proceed with routing the non-gaseous emissions from the treatment tanks 67 to the waterway 66 for discharge. It should be appreciated that the design of the treatment tanks 67 may allow the continuous passage of the non-gaseous emissions (i.e. the wastewater stream) through the treatment tanks 67.

With respect to the sorbent of the subject disclosure, several exemplary embodiments are disclosed. These exemplary embodiments are just a few examples and do not represent an exhaustive list of potential variations on the theme.

As noted above, one exemplary sorbent is elemental zinc powder. Zinc powder is made from elemental zinc. Zinc can come in the form of powders or in the form of granules. One method that can be used to extend the effective life of the zinc powder and/or granules at elevated temperatures for some gaseous emission applications and reduce and/or prevent premature oxidation is to mix or coat the granules and/or powder with a solid acid such as sulfamic acid, citric acid, or other organic acids. The powder/acid mixture can be injected into gaseous emissions (e.g. flue gas streams) and/or placed in an appropriate exemplary embodiment of the reverse venturi apparatus 15.

Optimal particle size for the zinc powder ranges from 0.5 nanometers to 7,500 microns. In addition, it has been found that a powder mixture with a range of different size particles is beneficial, especially if the particle sizes range from 0.5 nanometers to 7,500 microns. Similarly, the optimal particle size for zinc granules ranges from 7,500 microns to 3.0 inches. In addition, it has been found that a granule mixture with a range of different size granules is beneficial, especially if the granule sizes range from 7,500 microns to 3.0 inches.

In another exemplary embodiment, the sorbent is CZTS, which has the elemental formula of Cu₂ZnSnS₄. CZTS may also include other phases of copper, zinc, tin, and sulfur, which are also beneficial. CZTS and/or the associated phases of copper, zinc, tin, and sulfur may be blended in stoichiometric proportions and then mechanochemical compounding may be performed in a mill. Further still, the CZTS may be blended with equal proportions of any one of several clays such as bentonite or zeolite and calcium hydroxide (CaOH). The optimal particle size for CZTS powder ranges from 0.5 nanometers to 7,500 microns. It has been found in testing and development that CZTS powder mixtures with a range of different size particles is beneficial, especially if the particle sizes ranges from 0.5 nanometers to 7,500 microns. In applications where specialized CZTS granules are preferred, the optimal granule size has been found to range from 7,500 microns to 3.0 inches. In addition, it has been found that CZTS granule mixtures with a range of different size granules is beneficial, especially if the size of the granules ranges from 7,500 microns to 3.0 inches.

For most contaminants, the CZTS is most efficient at the smallest particle size within the above stated ranges and when the highest amount of CZTS in the metallic phase is present. It should be appreciated that during the manufacture of CZTS, a complete transformation of the mixture of copper, zinc, tin, and sulfur to CZTS does not take place, but is a mixture of phases (e.g. danbaite (CuZn₂) and tin sulfur (SnS)).

In one exemplary manufacturing method for CZTS, copper, zinc, tin, and sulfur are added to a mill in no particular order. Milling is accomplished using either a ball mill or some type of attrition mill or a combination of milling equipment which in sequential combination achieve the desired particle size. Exemplary starting particle size ranges from 325 standard mesh screens to 100 standard mesh screens, where 1 standard mesh screen equals 7,500 microns. The received particles are further weighed in a predetermined molar ratio of copper:zinc:tin:sulfur=1.7:1.2:1.0:4.0. After confirming mesh size and molar ratio, the particles are mechanochemically compounded into CZTS and its other phases by milling. Milling time is controlled to achieve optimum properties for specific applications. It should also be appreciated that milling can be accomplished using a wet milling process by adding a suitable solvent such as glycol ether, ethylene glycol, ammonia, or other alcohols or by dry milling, which is performed in an inert gas atmosphere.

During the milling, intermittent sampling takes place to determine particle size using a particle size analyzer, and an SEM, XRD, or Raman to determine percent phase transformation. The mill ball size is important and has been shown in testing to be optimized with a ball-to-powder weight ratio (charge ratio) of at least 5:1. The milling balls are best made of steel, ceramic, zirconia or any other material which achieves the size and/or phase transformations without contaminating the final product. When wet milling is used, the CZTS is dried. The CZTS is then blended further using a ribbon blender, V-blender, or any other suitable blender in order to blend in equal portions of bentonite or zeolite and calcium hydroxide.

In accordance with the methods described above, the sorbent may be introduced into gaseous emissions where the gaseous emissions are at a temperature of approximately 750 degrees Fahrenheit or less. The sorbent may be introduced into the gaseous emissions by any one of several methods such as, but not limited to, injection, fluid beds, coated filters, and traps. The method of introduction can be chosen based on existing emissions control systems in the plant to facilitate retro-fitting. One convenient method may be where CZTS is injected into the gaseous emissions in place of activated carbon, where the same injection equipment may be used with or without modification.

In some applications, the treatment of gaseous emissions may be optimized when CZTS is blended with bentonite for effective contaminant removal. Alternatively, the treatment of non-gaseous emission application may be optimized when CZTS is blended with Zeolite. In addition to the specific material blended with CZTS, the proportions of the blend may be application specific in order to provide optimized contaminant removal capabilities.

As shown in FIGS. 18A-B, where CZTS is used to treat gaseous emissions, the fabric filter unit 50 should be placed downstream of the CZTS introduction point 55, 56 so that the fabric filter unit 50 captures sorbent particles and increases the contact time that the gaseous emissions have with the sorbent. Deposition of the sorbent on the fabric filters (i.e. bags) of the fabric filter unit 50 allows additional contact time between the gaseous emissions and the sorbent and allows the sorbent to be collected for subsequent reclamation. The small particle size of the sorbent allows the sorbent to be carried along in the flow of gaseous emissions stream like dust being carried by the wind. During the period of time that the sorbent is carried in the flow of gaseous emissions, the sorbent comes in contact with contaminants also traveling in the flow of gaseous emissions and thusly can chemically react with and bind to the sorbent. Upon reaching the fabric filter unit 50, the gaseous emissions continue to pass through the filters in the fabric filter unit 50 while the particles of combined sorbent and contaminants are sized too large to pass through the filters. When the CZTS particles are less than 10 microns, it may be necessary to pre-coat the filters in the fabric filter unit 50 with a larger size CZTS particle, activated carbon, talc, lime, or other appropriate substance so the smaller CZTS particles do not pass through the filters. Alternative, a lower micron size rated filter may be used in the fabric filter unit 50.

In other applications for non-gaseous emissions, CZTS may be introduced into the treatment tanks 67 illustrated in FIG. 20. In this configuration, the CZTS is optimally introduced into the treatment tanks 67 with good agitation for a period of time, then the non-gaseous emissions (e.g. wastewater) undergoes pH adjustment, flocculation, and filtering before discharge. Afterwards, the CZTS in the treatment tanks 67 can undergo a reclamation process where the contaminants are harvested away from the CZTS. Used CZTS can be reclaimed by either leaching mercury from the CZTS or by vacuum distillation. The harvested contaminants may then be re-used in other industries. The CZTS also provides the benefit of being able to reduce nitrate and nitride levels in the non-gaseous emissions.

The water discharge regulations established by the EPA, which become effective in 2016, are much more stringent than those for air. Some of the current EPA water regulation levels listed in nanograms/Liter (ng/L), micrograms/Liter (μg/L), and/or grams/Liter are: mercury @ 119 ng/L; arsenic (As) @ 8 μg/L; selenium (Se) @ 10 μg/L; nitrogen dioxide (NO₂) and nitrate (NO₃) @ 0.13 g/L. Other heavy metals such as lead (Pb) and cadmium (Cd) also have proposed EPA restrictive levels. In many existing plants, water with contamination levels above allowable discharge regulations are routed to holding ponds and/or other types of sludge holding reservoirs of one kind or another. CZTS can treat solids in holding ponds by the same methods as disclosed herein for treating non-gaseous emissions. Depending on the ionic form of the heavy metal, sludge composition, and/or pH, the contact time for the CZTS in the holding pond can be appropriately adjusted. Adequate pH adjustment, flocculation, and subsequent filtering will allow for normal discharge, disposal, and/or use in other industries, none of which was previously possible.

It should be appreciated that the sorbents disclosed herein do not contain any loose carbon, including the activated carbon currently used in the art. As a result, none of the metal sulfides produced as by-products of the disclosed methods are leachable. Therefore, these by-products have valuable industrial use in gypsum wallboard and cement applications. EPA leach testing on metal sulfides is well known and use in these products is well documented.

Although activated carbon may be used in some alternative configurations, the limited use of activated carbon in these variations does not allow for the activated carbon to escape into the emissions. For example, in one configuration, activated carbon may be embedded in the filters of the fabric filter unit 50. This activated carbon is not free to escape into the flow of gaseous emissions. Another limited use of activated carbon is possible where the activated carbon coats the CZTS in its crystalline form, producing CZTS with a thin layer of carbon on the order of 1.0 nanometer in thickness or less. This helps to encourage the capture of extraordinarily small metallic vapor particles of mercury. In a similar fashion, the CZTS crystalline form can be coated with a nanometer-like thin layer of zeolite or other coatings to specifically target a specific hazardous contaminant for specialized applications. Again, the activated carbon in this example is not free to escape into the flow of gaseous emissions. In another configuration shown in FIG. 33, the reverse venturi fluidized bed apparatus includes provisions for cleaning and recycling the sorbent in the form of a series of sorbent recycling subsystems for CZTS sorbents, CZTS-Alloy sorbents, and/or CZTS-Mixture sorbents. Such CZTS-Mixture sorbents may include, but are not limited to granulated iron oxide (GFO) coated with CZTS and carbon-based sorbents coated with CZTS.

Referring to FIG. 21, a graph illustrates the percentages of contaminants removed from emissions as a result of existing emissions control systems and the reverse venturi apparatus and the method disclosed herein. A 90% contaminant removal level 78 is currently established for gaseous emissions by the EPA. Existing emissions control systems 79 are effective to remove between 88%-90% of hazardous contaminants. However, the EPA has been raising the minimum percentage contaminant removal required over the years to the point that many existing emissions control systems are no longer able to meet the requirements and many other existing emissions control systems just meet the requirements while operating at their maximum removal capabilities available under the current technology.

Still referring to FIG. 21, the exemplary emissions control system 80 may either be a new emissions control system based upon the reverse venturi apparatus, the sorbents, and/or methods disclosed herein or it may be an existing emissions control system which has been modified and augmented to include the reverse venturi apparatus, the sorbents, and methods disclosed herein. Testing has confirmed that the exemplary emissions control system 80 is effective and capable of removing at least 98% of hazardous contaminants, which is well above the current EPA regulated levels.

Referring to FIG. 22 and FIG. 24, an exemplary method of emissions control is illustrated with contaminated gaseous source 150 introduced into the system through one or more pre-fluidized bed filters 151, through fluidized bed 152, through one or more post fluidized bed filters 153, and through a system discharge 154, which releases the gaseous discharge with an environmentally controlled release through a stack 155. It should be appreciated that it is not always necessary to first pass contaminated gaseous source 150 through one or more pre-fluidized bed filters 151; however, application specific requirements may dictate the need for one or more pre-fluidized bed filters 151.

Fluidized bed 152 has a reverse venturi shape, which has a specific length L to diameter D size ratio of between 2.9:1 as a minimum and 9.8:1 as a maximum. This ratio is optimized for extended residence flow time of contaminated gaseous source 150 in fluidized bed 152, which is filled with specialized sorbent such as reactive material 164. Reactive material 164 is a sorbent including a copper, zinc, tin, sulfur (CZTS) compound and/or an alloy thereof. The preferred exemplary length L to diameter D ratio for fluidized bed 152 is 4.4:1, which has been determined through trial and error testing.

Preferably, the fluidized bed 152 has a predominately round cross section. While not shown in FIG. 24, one or more of the various baffles and/or other application specific flow restriction obstacles disclosed herein can be incorporated into the fluidized bed 152. Fluidized bed 152 also features predominately outward extending convex ends 168 and 169 to promote extended residence flow time with minimized turbulent flow through reactive material 164. As contaminated gaseous source 150 flow enters fluidized bed 152 at entry port 165, intimate contact with reactive material 164 is initiated, resulting in random non-turbulent flow 166. Random non-turbulent flow 166 is turned back upon itself due to predominately outward extending convex ends 168 and 169, resulting in extended residence time in fluidized bed 152 before the non-turbulent flow 166 exits from fluidized bed 152 through exit port 167. Reactive material 164 promotes random non-turbulent flow 166, which is a randomized torturous flow path for contaminated gaseous source 150. It should be appreciated that length L of the fluidized bed 152 is not inclusive of the convex ends 168 and 169.

Fluidized bed 152 has a side outlet port 170 leading to a sorbent cleaning station 156. Sorbent cleaning station 156 has an option to remove exhausted sorbent 157 from the system for disposal. In addition, captured contaminated elements 158 captured from contaminated gaseous source 150 by reactive material 164 and separated from reactive material 164 in sorbent cleaning station 156 can be disposed and/or recycled. Sorbent cleaning station 156 returns cleaned reactive material 164 back to fluidized bed 152 through sorbent return port 159. Bulk refill sorbent container 168 provides a makeup volume of reactive material 164 as necessary to replace removed exhausted sorbent 157. System discharge 154 provides a gaseous discharge through an environmentally controlled release out of exhaust stack 155. Additional discharge of captured waste 160 may also be provided by additional sorbent recycling subsystems (FIG. 33).

Referring to FIG. 23 and FIG. 24, an exemplary method of emissions control is illustrated with contaminated non-gaseous source 161 introduced into the system through one or more pre-fluidized bed filters 151, through fluidized bed 152, through one or more post fluidized bed filters 153, and through a system discharge 154, which releases the non-gaseous discharge with an environmentally controlled release 162. It should be appreciated that it is not always necessary to first pass contaminated non-gaseous source 161 through one or more pre-fluidized bed filters 151; however, application specific requirements may dictate the need for one or more pre-fluidized bed filters 151.

Fluidized bed 152 has a reverse venturi shape which has a specific length L to diameter D size ratio of between 2.9:1 as a minimum and 9.8:1 as a maximum, which is optimized for extended residence flow time of contaminated non-gaseous source 161 in fluidized bed 152, which is filled with specialized sorbent such as reactive material 164. Reactive material 164 is a sorbent including a copper, zinc, tin, sulfur (CZTS) compound and/or an alloy thereof. The preferred exemplary length L to diameter D ratio for fluidized bed 152 is 4.4:1, which has been determined through trial and error testing.

Preferably, the fluidized bed 152 also features predominately outward extending convex ends 168 and 169 to promote extended residence flow time with minimized turbulent flow through reactive material 164. As contaminated non-gaseous source 161 flow enters fluidized bed 152 at entry port 165, intimate contact with reactive material 164 is initiated, resulting in random non-turbulent flow 166. Random non-turbulent flow 166 is turned back upon itself due to predominately outward extending convex ends 168 and 169 resulting in extended residence time in fluidized bed 152 before exiting from fluidized bed 152 through exit port 167. Reactive material 164 promotes random non-turbulent flow 166, which is a randomized torturous flow path for contaminated non-gaseous source 161. It should be appreciated that length L of the fluidized bed 152 is not inclusive of the convex ends 168 and 169.

Preferably, the fluidized bed 152 has a predominately round cross section. While not shown in FIG. 24, one or more of the various baffles and/or other application specific flow restriction obstacles disclosed herein can be incorporated into the fluidized bed 152. Fluidized bed 152 has a side outlet port 170 leading to a sorbent cleaning station 156. Sorbent cleaning station 156 has an option to remove exhausted sorbent 157 from the system for disposal. In addition, captured contaminated elements 158 captured from contaminated non-gaseous source 161 by reactive material 164 and separated from reactive material 164 in sorbent cleaning station 156 can be disposed and/or recycled. Sorbent cleaning station 156 provides return to cleaned reactive material 164 back to fluidized bed 152 through sorbent return port 159. Bulk refill sorbent container 168 provides makeup volume of reactive material 164 as necessary to replace removed exhausted sorbent 157. System discharge 154 provides a non-gaseous discharge through an environmentally controlled release 162. Additional discharge of captured waste 163 is also provided.

Referring to FIG. 25, an exemplary method is shown for passing contaminated gaseous emissions 250 through one or more pre-filters 251, through the fluidized bed 253, through one or more post filters 255, through system discharge 256, and finally released as a controlled release gaseous emission through exhaust stack 257 and/or through a waste disposal process 262. The fluidized bed 253 is bisected by longitudinal plane 290. Entry port P3 and exit port P4 are configured to receive and discharge the gaseous emissions when the fluidized bed 253 is positioned with longitudinal plane 290. Obstructions (not shown) interior to fluidized bed 253 provide a preferred torturous flow path particularly well suited for gaseous emissions when introduced through entry port P3 and discharged through exit port P4. The entry port P3 and the exit port P4 are positioned above the longitudinal plane 290 of the fluidized bed 253.

As shown in FIG. 25, the fluidized bed 253 can be mounted on truck 254 and is configured to tilt the fluidized bed 253 about a pivot point 252. When gaseous emissions are to be processed in the fluidized bed 253, the longitudinal plane 290 of the fluidized bed 253 is substantially horizontal. Sorbent cleaning station 258 is provided in fluid communication with outlet port P5 of the fluidized bed 253, where contaminated particles captured by the sorbent are removed. Removed contaminates can be recycled or disposed of through station 261. Exhausted Sorbent is disposed of through station 259 and the cleaned sorbent is recycled back to the fluidized bed 253 through return port P6 from sorbent return station 260.

Referring to FIG. 26, an exemplary method is shown for passing contaminated non-gaseous emissions 295 through one or more pre-filters 251, through the fluidized bed 253, through one or more post filters 255, through system discharge 256, and finally released as a controlled environmental non-gaseous release 273 and/or through a waste disposal process 274. Entry port P2 and exit port P1 are configured to receive and discharge the non-gaseous emissions. Obstructions (not shown) interior to fluidized bed 253 provide a preferred torturous flow path particularly well suited for non-gaseous emissions when introduced through entry port P2 and exit port P1. The entry port P2 and the exit port P1 are bisected by the longitudinal plane 290 of the fluidized bed 253 (i.e. are aligned with longitudinal plane 290 of the fluidized bed 253).

When non-gaseous emissions are to be processed in the fluidized bed 253, the longitudinal plane 290 of the fluidized bed 253 is substantially vertical. Sorbent cleaning station 258 is provided in fluid communication with outlet port P5 of the fluidized bed 253, where contaminated particles captured by the sorbent are removed. Removed contaminates can be recycled or disposed of through station 261. Exhausted Sorbent is disposed of through station 259 and the cleaned sorbent is recycled back to the fluidized bed 253 through return port P6 from sorbent return station 260.

Referring to FIG. 27, a matrix is shown wherein the disclosed preferred reactive CZTS Alloy sorbents 341 are compared to other sorbents, including Activated Carbon 342 and Zeolite 343. Contaminates 367 are listed as predominate types, including Nitrogen 368, Phosphates 369, Heavy Metals 370, Sulfur 371, Mercury 372, and Selenate 373. Contaminates 367 are further listed with each sorbent enumerated in gaseous emissions 344, 346, and 348 compared to non-gaseous emissions 345, 347, and 349.

The reactive CZTS Alloy sorbents 341 are confirmed by testing to be effective in the capture and removal of contaminates 367 in gaseous 344 emissions and/or non-gaseous 345 emissions. In contrast, Activated Carbon 342 is not effective in the capture or removal of contaminates 367 in gaseous emissions 346 and/or non-gaseous emissions 347. Similarly, Zeolite 343 is not effective in the capture or removal of contaminates 367 in gaseous emissions 348 and/or non-gaseous emissions 349.

Referring to FIG. 28, an expanded list of sorbents is shown including the reactive CZTS Alloy sorbents 351 of the subject disclosure and other sorbents, including Caustics 350, Ferric Oxide 355, and Zeolite 356. The reactive CZTS Alloy sorbents 351 include a CZTS Alloy of Sulfur (S) 352, a CZTS Alloy of Selenate (S) 353, and a CZTS Alloy of Ferrous Oxide 354. The CZTS Alloy sorbents 351 collectively react effectively with the following groups of contaminates: Selenate 357, Total Ionized Sulfurs 358, Total Ionized Nitrogens 359, and Total Ionized Phosphates 360. The reactive CZTS Alloy sorbents 351 are able to capture and remove these contaminates from both gaseous and non-gaseous emissions.

In contrast, Caustics 350 are only effective with Total Ionized Sulfurs 358. Ferric Oxide 355 is only effective with Selenate 357 and has very slow reactive characteristics with Total Nitrogens 359 and Total Ionized Phosphates 360 (and work with non-gaseous emissions only). Zeolite 356 is only effective with Total Ionized Nitrogens 359 and Total Ionized Phosphates 360. As a result, known sorbents such as Caustics 350, Ferric Oxide 355, and Zeolite 356 have limited effective characteristics compared to the broad-spectrum characteristics of the reactive CZTS Alloy sorbents 351 disclosed herein. Even when known sorbents have a level of effectiveness, they all fall short of the effectiveness level of the reactive CZTS Alloy sorbents 351 disclosed herein.

Referring to FIG. 29, matrix 364 shows the capability of prior art sorbents 365 to be post processed after being used in emissions control systems to capture and remove contaminates 367 including Nitrogens 368, Phosphorous 369, Heavy Metals 370, Sulfurs 369, Mercury 372, and Selenates 373. The capability to separate these contaminates 367 from the prior art sorbent in gaseous emissions 374 and/or non-gaseous emissions 375 is very poor and virtually non-existent except for Nitrogens 368 in gaseous emissions 374. Similarly, matrix 364 shows the capability to reuse the prior art sorbents 366 after separation of contaminates 367 is also virtually non-existent except for gaseous emissions 376 containing Nitrogens 368.

Referring to FIG. 30, matrix 378 shows the capability of the reactive CZTS Alloy sorbents 339 disclosed herein to be post processed after being used in emissions control systems capture and remove contaminates 367 including Nitrogens 368, Phosphorous 369, Heavy Metals 370, Sulfurs 369, Mercury 372, and Selenates 373. The capability to separate contaminates 367 in gaseous emissions 374 and/or non-gaseous emissions 375 emissions from the disclosed reactive CZTS Alloy sorbents 339 is particularly advantageous because it means the contaminates 367 can be more readily disposed of or recycled and because the reactive CZTS Alloy sorbents 339 can be reused in emissions control systems (as shown in matrix 378). Specifically, matrix 378 shows the capability to reuse the reactive CZTS Alloy sorbents 340 disclosed herein after they are separated from contaminates 365 in gaseous emissions 376 and non-gaseous emissions 377.

Referring to FIG. 31, a block diagram shows a system and method for removing contaminates from gaseous emissions 250. Gaseous emissions 250 are monitored and analyzed in step 379 to determine the types and levels of contaminates in the gaseous emissions 250. Monitoring can be systematic intermittent spot checks at periodic intervals or continuous in-line monitoring and analysis. Based on the types and/or levels of contaminates resident in the gaseous emission 250 determined by step 379, emissions flow is routed through pre-filter inlet manifold 380 so that the gaseous emissions 250 are further routed through appropriate pre-filters 381, 382, 383, and/or 384. Selection of the appropriate pre-filters 381, 382, 383, and/or 384 is accomplished through the selection method illustrated in FIG. 28.

The pre-filters shown in FIG. 31 are filled with the reactive CZTS Alloy sorbents 351 shown in FIG. 28. For example, pre-filter 381 is filled with the CZTS Alloy of Sulfur (S) 352 shown in FIG. 28. Pre-filter 382 is filled with the CZTS Alloy of Selenate (S) 353 shown in FIG. 28. Pre-filter 383 is filled with the CZTS Alloy of Ferrous Oxide 354 shown in FIG. 28. Pre-filter 384 is filled with a combination of CZTS Alloy sorbents 352, 353, and/or 354. Additional pre-filters can be added to pre-filter inlet manifold 380, each filled with a different combination of CZTS Alloy sorbents 352, 353, and/or 354, combined to effectively treat specific levels and/or types of contaminates resident in gaseous emissions 250.

After contaminated gaseous emissions 250 are routed through appropriate pre-filters, pre-filter outlet manifold 385 routes emissions into fluidized bed 253. For gaseous emissions 250, the housing of the fluidized bed 253 is arranged in an orientation that is substantially parallel to platform 271. Contaminates are separated from the sorbent in step 258 and returned to the fluidized bed 253 through sorbent return port 260.

After gaseous emissions 250 exit fluidized bed 253, post-filter monitoring step 386 determines the new levels and/or types of contaminates remaining in the gaseous emissions 250 and routes the gaseous emissions 250 through post-filter inlet manifold 387. Selection of the appropriate post-filters 388, 389, 390, and/or 391 is accomplished through the selection method illustrated in FIG. 28. The post-filters shown in FIG. 31 are filled with the reactive CZTS Alloy sorbents 351 shown in FIG. 28. For example, post-filter 388 is filled with the CZTS Alloy of Sulfur (S) 352 shown in FIG. 28. Post-filter 389 is filled with the CZTS Alloy of Selenate (S) 353 shown in FIG. 28. Post-filter 390 is filled with the CZTS Alloy of Ferrous Oxide 354 shown in FIG. 28. Post-filter 391 is filled with a combination of CZTS Alloy sorbents 352, 353, and/or 354. Post-filter outlet manifold 392 routes the gaseous emissions 250 to gaseous system discharge 256 a where some of the gaseous emissions 250 are expelled through controlled gaseous release stack 257 and some of the gaseous emissions 250 are expelled through a proper waste disposal step 262.

Additional post-filters can be added to post-filter inlet manifold 387, each filled with a different combination of CZTS Alloy sorbents 352, 353, and/or 354, combined to effectively treat specific levels and/or types of contaminates resident in gaseous emissions 250.

All the pre-filters 381, 382, 383, 384 and post-filters 388, 389, 390, 391 can be separately routed through sorbent cleaning step 258 and sorbent return port 260. Step 258 includes separating contaminates from the CZTS Alloy sorbents 351 so that the contaminates can be recycled and/or properly collected for disposal 261. Any exhausted CZTS Alloy sorbent 351 can be disposed through disposal step 259. Replacement of specific CZTS Alloy sorbents 351 to each specific pre-filter 381, 382, 383, 384 and/or post-filter 388, 389, 390, 391 may be implemented after step 258. Specific routing diagrams and/or schematics for routing sorbent from the pre-filters 381, 382, 383, 384 and/or post-filters 388, 389, 390, 391 to and from the sorbent cleaning step 258 is not shown.

Referring to FIG. 32, a block diagram shows a system and method for removing contaminates from non-gaseous emissions 295. Non-gaseous emissions 295 are monitored and analyzed in step 379 to determine the types and levels contaminates in the non-gaseous emissions 295. Monitoring can be systematic intermittent spot checks at periodic intervals and/or continuous in-line monitoring and analysis. Based on the types and/or levels of contaminates resident in the non-gaseous emission 295 determined by step 379, emissions flow is routed through pre-filter inlet manifold 380 so that the non-gaseous emissions 295 are further routed through appropriate pre-filters 381, 382, 383, and/or 384. Selection of the appropriate pre-filters 381, 382, 383, and/or 384 is accomplished through the selection method illustrated in FIG. 28.

The pre-filters shown in FIG. 32 are filled with the reactive CZTS Alloy sorbents shown in FIG. 28. For example, pre-filter 381 is filled with the CZTS Alloy of Sulfur (S) 352 shown in FIG. 28. Pre-filter 382 is filled with the CZTS Alloy of Selenate (S) 353 shown in FIG. 28. Pre-filter 383 is filled with the CZTS Alloy of Ferrous Oxide 354 shown in FIG. 28. Pre-filter 384 is filled with a combination of CZTS Alloy sorbents 352, 353, and/or 354. Additional pre-filters can be added to pre-filter inlet manifold 380, each filled with a different combination of CZTS Alloy sorbents 352, 353, and/or 354, combined to effectively treat specific levels and/or types of contaminates resident in non-gaseous emissions 295.

After contaminated non-gaseous emissions 295 are routed through appropriate pre-filters, pre-filter outlet manifold 385 routes emissions into fluidized bed 253. For non-gaseous emissions 295, the housing of the fluidized bed 253 is arranged in an orientation that is substantially perpendicular to platform 271. Contaminates are separated from the sorbent in step 258 and returned to the fluidized bed 253 through sorbent return port 260.

After non-gaseous emissions 295 exit fluidized bed 253, post-filter monitoring step 386 determines the new levels and/or types of contaminates remaining in the non-gaseous emissions 295 and routes the non-gaseous emissions 295 through post-filter inlet manifold 387. Selection of the appropriate post-filters 388, 389, 390, and/or 391 is accomplished through the selection method illustrated in FIG. 28. The post-filters shown in FIG. 32 are filled with the reactive CZTS Alloy sorbents 351 shown in FIG. 28. For example, post-filter 388 is filled with the CZTS Alloy of Sulfur (S) 352 shown in FIG. 28. Post-filter 389 is filled with the CZTS Alloy of Selenate (S) 353 shown in FIG. 28. Post-filter 390 is filled with the CZTS Alloy of Ferrous Oxide 354 shown in FIG. 28. Post-filter 391 is filled with a combination of CZTS Alloy sorbents 352, 353, and/or 354. Post-filter outlet manifold 392 routes the non-gaseous emissions 295 to non-gaseous system discharge 256 b where some of the non-gaseous emissions 295 are expelled through environmentally controlled non-gaseous release 273 and some of the non-gaseous emissions 295 are expelled through a proper waste disposal step 262. Additional post-filters can be added to post-filter inlet manifold 387, each filled with a different combination of CZTS Alloy sorbents 352, 353, and/or 354, combined to effectively treat specific levels and/or types of contaminates resident in non-gaseous emissions 295.

All the pre-filters 381, 382, 383, 384 and post-filters 388, 389, 390, 391 can be separately routed through sorbent cleaning step 258 and sorbent return port 260. Step 258 includes separating contaminates from the CZTS Alloy sorbents 351 so that the contaminates can be recycled and/or properly collected for disposal 261. Any exhausted CZTS Alloy sorbents 351 can be disposed through disposal step 259. Replacement of specific CZTS Alloy sorbents 351 to each specific pre-filter 381, 382, 383, 384 and/or post-filter 388, 389, 390, 391 may be implemented after step 258. Specific routing diagrams and/or schematics for routing sorbent from the pre-filters 388, 389, 390, 391 and/or post-filters 388, 389, 390, 391 to and from the sorbent cleaning step 258 is not shown.

Referring to FIG. 33, an exemplary emission control system is illustrated. Contaminated emissions are introduced into fluidized bed 152 via entry port 165. It should be appreciated that the emissions may first pass through one or more pre-fluidized bed filters 151 (FIGS. 22 and 23) depending on application specific requirements.

The fluidized bed 152 has a housing 16 with a reverse venturi shape, which has a specific length L to diameter D size ratio of between 2.9:1 as a minimum and 9.8:1 as a maximum. This ratio is optimized for extended residence flow time of contaminated emissions in fluidized bed 152, which is filled with specialized reactive material 164, which includes one or more sorbents. The preferred exemplary length L to diameter D ratio for fluidized bed 152 is 4.4:1, which has been determined through trial and error testing. One or more exemplary fluidized beds 152 can be linked in series or in parallel as may be required for application specific requirements.

Preferably, the fluidized bed 152 has a predominately round cross section. While not shown in FIG. 33, one or more of the various baffles and/or other application specific flow restriction obstacles disclosed herein can be incorporated into the fluidized bed 152. Fluidized bed 152 also features predominately outward extending convex ends 168, 169 to promote extended residence flow time with minimized turbulent flow through reactive material 164. As the contaminated emissions flow enters fluidized bed 152 at entry port 165, intimate contact with reactive material 164 is initiated, resulting in random non-turbulent flow 166. Random non-turbulent flow 166 is turned back upon itself due to the predominately outward extending convex ends 168, 169, resulting in extended residence time in fluidized bed 152 before the non-turbulent flow 166 exits from fluidized bed 152 through exit port 167. Reactive material 164 promotes random non-turbulent flow 166, which is a randomized torturous flow path for contaminated emissions. It should be appreciated that length L of the fluidized bed 152 is not inclusive of the convex ends 168, 169.

Fluidized bed 152 includes at least one monitoring sensor station 421 (i.e., a first monitoring sensor) that provides data, status, and feedback on the operating parameters. Monitoring sensor station(s) 421 are equipped to monitor emission flow levels, pressure, velocity, temperature, and many other relevant parameters associated with the emissions control system. Based on feedback information, some automatic adjustments can be made by the equipment, while other process and/or system parameters may require manual adjustments. Monitoring sensor stations 421 provide information about the efficiency of the sorbent inside fluidized bed 152 and help determine when it is time to clean and/or rejuvenate the sorbent.

In an exemplary embodiment of the subject disclosure, fluidized bed 152 has at least one side outlet port 403, 409, 415 leading to sorbent recycling subsystems 400, 401, 402 respectively. The sorbent recycling subsystems 400, 401, 402 shown in FIG. 33 are positioned external to fluidized bed 152, but alternatively, they can be installed inside fluidized bed 152.

Fluidized bed 152 includes at least one closed loop sorbent exit port monitoring sensor station 422 and at least one closed loop sorbent return port monitoring sensor station 423 that provide data, status, and feedback on the operating parameters. Monitoring sensor station 422 is configured to monitor emission flow levels, pressure, velocity, temperature, and many other relevant parameters associated with the emissions control system. Based on feedback information, some automatic adjustments can be made using programable equipment, while other process and/or system parameters may require manual adjustments. Monitoring sensor 423 identifies sorbent conditions as the sorbent passes through one of the exit ports 403, 409, or 415 and into subsystem 400, 401, or 402 respectively. Monitoring sensor station 423 is configured to monitor emission flow levels, pressure, velocity, temperature, and many other relevant parameters associated with the emissions control system.

Based on feedback information, some automatic adjustments can be made using programable equipment, while other process and/or system parameters may require manual adjustments. Monitoring sensor 423 identifies sorbent conditions as it passes through one of the return ports 407, 414, or 420 of subsystem 400, 401, or 402 respectively after cleaning and/or rejuvenation. Monitoring sensor station 424 (i.e., a second monitoring sensor) is configured to monitor emission flow levels, pressure, velocity, temperature, and many other relevant parameters associated with the emissions control system. Based on feedback information, some automatic adjustments can be made using programable equipment, while other process and/or system parameters may require manual adjustments. Monitoring sensor 424 monitors conditions and resulting volume of sorbent 164 as it is processed in station 404, 410, or 416 within subsystem 400, 401, or 402 respectively as the cleaning and/or rejuvenation process occurs. Monitoring sensors 421, 422, 423, 424 are configured to cooperate with each other and provide process conditions and/or parameter adjustments to establish and maintain consistency and optimum sorbent efficiency at each station in the emissions control system. Monitoring of sorbent within subsystems 400, 401, 402 will determine when and how much makeup sorbent is required from station 408, 413, and 419 respectively.

In another exemplary embodiment (not shown), cleaning and/or rejuvenation subsystems are installed and configured internal to fluidized bed 152. In this configuration, the monitoring sensors 421, 422, 423, 424 and functions of the sorbent recycling subsystems 400, 401, 402 occur internal of the fluidized bed 152.

Still referring to FIG. 33, fluidized bed 152 will be filled with sorbent, which is CZTS, a CZTS-Alloy, a CZTS-Mixture, or some combination of all three categorizations of sorbent. CZTS is a compound with four element ingredients (Copper, Zinc, Tin, Sulfur). These elements are pure chemical substances made of the same type of atom. A CZTS compound contains atoms of Copper, Zinc, Tin, and Sulfur that are chemically combined together in a fixed ratio to form a stable compound. Elements cannot be broken down into simpler substances by chemical reactions. Compounds can be separated and/or broken down into simpler substances by chemical methods and/or chemical reactions. Electrons of atoms are shared between elements in the formation of compounds.

An alloy includes two or more chemical elements or compounds, of which at least one is a metal. CZTS-Alloys include the four elements of Copper, Zinc, Tin, and Sulfur, as well as at least one additional element or compound that is a metal, to form a CZTS-Alloy. The electrons of the at least one additional element or compound are shared with the CZTS compound to form a new compound in the form of an alloy.

CZTS-Mixtures include the CZTS compound combined with at least one additional element or compound. However, in contrast to CZTS-Alloys, the electrons of CZTS compound and the at least one additional metallic element or compound are not shared. The components of CZTS-Mixtures do not share the electrons of atoms. A common example of a mixture is dissolving a salt compound (NaCl) into a water compound (H₂O). The mixture will be a solution, but the atoms of salt and water will not share any electrons between each other. Therefore, no new compound is formed, and the two compounds of salt and water are simply mixed together with no chemical bonding taking place.

When fluidized bed 152 is filled with reactive material 164 that includes CTZS sorbent, then sorbent recycling subsystem 400 is used to maintain optimum process conditions for the CZTS sorbent. Sorbent discharge port 403 allows transfer of sorbent into sorbent recycling station 404. The sorbent recycling station 404 in subsystem 400 includes one or more chemical reagents that separate contaminants from the CZTS sorbent as part of a cleaning and rejuvenation process. By way of non-limiting example, the chemical reagents used in the sorbent recycling station 404 may be selected from a group of fatty alcohols. Spent and/or exhausted CZTS sorbent can be disposed of through sorbent disposal station 405. Emission contaminants removed from emissions can be recycled back into various industries through contaminant disposal port 406. Bulk refill station 408, such as a container of new/fresh sorbent, provides a makeup supply of CZTS sorbent that replaces the sorbent that has been removed and/or lost during the removal of contaminants from emissions. CZTS sorbent return port 407 completes a closed loop back into fluidized bed 152.

The cleaning and/or rejuvenation of CZTS can be accomplished using simple lipids, such as glycerin. Lipids containing phosphorous do not work as well because the phosphorous is essentially a contaminate itself. Lipids with a low pH can lead to decomposition of the CZTS and evolve hydrogen sulfide (H₂S), leaving the sorbent Sulfur-deficient. Accordingly, additional rejuvenation steps are required to efficiently use low pH lipids. Testing has determined a minimum optimum pH range of between 6.49-7.73 to avoid acidic degradation of CZTS. Testing has further determined a maximum pH is limited to 9.05 to avoid base degradation of CZTS. Glycolipids are preferred as their relative viscosity is lower and therefore make it easier to maximize contact with the sorbent and are easier to remove/separate from the sorbent after the cleaning and/or rejuvenation process is complete, especially when heat is applied. Glycolipids are also water soluble, so a dilute solution can be used. Lipids with carbon atoms with a hydroxyl group are preferred as an optimum lipid for cleaning and/or rejuvenation of CZTS.

As an alternative to glycerin, some benefits for cleaning and/or rejuvenation of CZTS can be realized using long chain alcohols (cetyl and stearyl alcohol) dissolved in hot water. However, glycerin is preferred over all other known cleaning and/or rejuvenation substances for CZTS.

Captured contaminates such as mercury are soluble in simple lipids. Therefore, saturated CZTS with contaminates can be sprayed in the cleaning and/or rejuvenation station 404 to extract and separate the contaminates from the CZTS. After separating the simple lipids with the soluble contaminates from the CZTS, a steam rinse and/or hot water rinse completes the process of the rejuvenation of CZTS. The rinse can be a pressurized rinse or a gravity flow rinse. This process completely cleans the CZTS of all contaminates and rejuvenates it to original condition so that it can be returned to fluidized bed 152 through return port 407.

In accordance with this process, the simple lipids are heated to an optimal temperature of between 85 degrees Celsius (° C.) and 110 degrees Celsius (° C.). The heated simple lipids are then sprayed on the saturated CZTS. Based on contact time, a lower effective temperature for heating the simple lipids of 5 degrees Celsius (° C.) above ambient and an upper effective temperature of 140 degrees Celsius (° C.) will work for the cleaning and/or rejuvenation of CZTS.

An alternative process to the use of simple lipids to separate contaminates from CZTS, which can be integrated into the cleaning and/or rejuvenation station 404, is the use of a vacuum dryer because mercury can be distilled and volatized. After contaminates are volatized in the vacuum dryer, the contaminates can be captured in filters and/or scrubbers. Scrubbers and filters can be especially effective when saturated in diluted simple lipids.

Contaminated simple lipids, which have been separated from CZTS, can be recycled after discharge from contaminant disposal port 406 in a process where contaminates are separated from the simple lipids by normal industry processes. After the separation of contaminates, the spent simple lipids can be burned, while the contaminates are separately collected for recycling back into industry uses and/or proper disposal. If any CZTS has been lost due to handling during the cleaning and/or rejuvenation process, bulk refill station 408 restores CZTS to proper volumes in fluidized bed 152.

When fluidized bed 152 is filled with reactive material 164 that includes CTZS-Alloy sorbent, then sorbent recycling subsystem 401 is used to maintain optimum process conditions for the CZTS-Alloy sorbent. Sorbent discharge port 409 allows transfer of sorbent into sorbent recycling station 410. The sorbent recycling station 410 in subsystem 401 includes one or more chemical reagents that separate contaminants from the CZTS-Alloy sorbent as part of a cleaning and rejuvenation process. By way of non-limiting example, the chemical reagents used in the sorbent recycling station 410 may be selected from a group of fatty alcohols. Spent and/or exhausted CZTS-Alloy sorbent can be disposed of through station 411. Emission contaminants removed from emissions can be recycled back into various industries through contaminant disposal port 412. Bulk refill station 413 provides a makeup supply of CZTS-Alloy sorbent that replaces the sorbent that has been removed and/or lost during the removal of contaminants from emissions. CZTS-Alloy sorbent return port 414 completes a closed loop back into fluidized bed 152.

The cleaning and/or rejuvenation of CZTS-Alloy can be accomplished using simple lipids, such as glycerin. Lipids containing phosphorous do not work as well because the phosphorous is essentially a contaminate itself. Lipids with a low pH can lead to decomposition of the CZTS-Alloys and evolve hydrogen sulfide (H₂S), leaving the sorbent Sulfur-deficient. Accordingly, additional rejuvenation steps are required to efficiently use low pH lipids. Testing has determined a minimum optimum pH range of between 6.49-7.73 to avoid acidic degradation of CZTS-Alloys. Testing has further determined a maximum pH is limited to 9.05 to avoid base degradation of CZTS-Alloys. Glycolipids are preferred as their relative viscosity is lower and therefore make it easier to maximize contact with the sorbent and are easier to remove/separate from the sorbent after the cleaning and/or rejuvenation process is complete, especially when heat is applied. Glycolipids are also water soluble, so a dilute solution can be used. Lipids with carbon atoms with a hydroxyl group are preferred as an optimum lipid for cleaning and rejuvenation of CZTS-Alloys.

As an alternative to glycerin, some benefits for cleaning and/or rejuvenation of CZTS-Alloys can be realized using long chain alcohols (cetyl and stearyl alcohol) dissolved in hot water. However, glycerin is preferred over all other known cleaning and/or rejuvenation substances for CZTS-Alloys.

Captured contaminates such as mercury are soluble in simple lipids. Therefore, saturated CZTS-Alloys with contaminates can be sprayed in the cleaning and/or rejuvenation station 410 to extract and separate the contaminates from the CZTS-Alloys. After separating the simple lipids with the soluble contaminates from the CZTS-Alloys, a steam rinse and/or hot water rinse completes the process of the rejuvenation of CZTS-Alloys. The rinse can be a pressurized rinse or a gravity flow rinse. This process completely cleans the CZTS-Alloys of all contaminates and rejuvenates it to original condition so that it can be returned to fluidized bed 152 through return port 414.

In accordance with this process, the simple lipids are heated to an optimal temperature of between 85 degrees Celsius (° C.) and 110 degrees Celsius (° C.). The heated simple lipids are then sprayed on the saturated CZTS-Alloys. Based on contact time, a lower effective temperature for heating the simple lipids of 5 degrees Celsius (° C.) above ambient and an upper effective temperature of 140 degrees Celsius (° C.) will work for the cleaning and/or rejuvenation of CZTS-Alloys.

An alternative process to the use of simple lipids to separate contaminates from CZTS-Alloys, which can be integrated into the cleaning and/or rejuvenation station 410, is the use of a vacuum dryer because mercury can be distilled and volatized. After contaminates are volatized in the vacuum dryer, the contaminates can be captured in filters and/or scrubbers. Scrubbers and filters can be especially effective when saturated in diluted simple lipids.

Contaminated simple lipids, which have been separated from CZTS-Alloys, can be recycled after discharge from contaminant disposal port 412 in a process where contaminates are separated from the simple lipids by normal industry processes. After separation of contaminates, the spent simple lipids can be burned, while the contaminates are separately collected for recycling back into industry uses and/or proper disposal. If any CZTS-Alloy has been lost due to handling during the cleaning and/or rejuvenation process, bulk refill station 413 restores CZTS-Alloy to proper volumes in fluidized bed 152.

When fluidized bed 152 is filled with reactive material 164 that includes CZTS-Mixture sorbent, then sorbent recycling subsystem 402 is used to maintain optimum process conditions for the carbon-based sorbent. Sorbent discharge port 415 allows transfer of sorbent into sorbent recycling station 416. The sorbent recycling station 416 in subsystem 402 includes one or more chemical reagents that separate contaminants from the carbon-based sorbent as part of a cleaning and rejuvenation process. By way of non-limiting example, the chemical reagents used in the sorbent recycling station 416 may be solvents such as Methyl Ethyl Ketone, Methylene Chloride, and/or Methanol. Spent and/or exhausted carbon-based sorbent can be disposed of through sorbent disposal station 417. Emission contaminants removed from emissions can be recycled back into various industries through contaminant disposal port 418. Bulk refill station 419 provides a makeup supply of carbon-based sorbent that replaces the sorbent that has been removed and/or lost during the removal of contaminants from emissions. Carbon-based sorbent return port 420 completes a closed loop back into fluidized bed 152.

The cleaning and/or rejuvenation of CZTS-Mixture can be accomplished using simple lipids, such as glycerin. Lipids containing phosphorous do not work as well because the phosphorous is essentially a contaminate itself. Lipids with a low pH can lead to decomposition of the CZTS-Mixture and evolve hydrogen sulfide (H₂S), leaving the sorbent Sulfur-deficient. Accordingly, additional rejuvenation steps are required to efficiently use low pH lipids. Testing has determined a minimum optimum pH range of between 6.49-7.73 to avoid acidic degradation of CZTS-Mixtures. Testing has further determined a maximum pH is limited to 9.05 to avoid base degradation of CZTS-Mixtures. Glycolipids are preferred as their relative viscosity is lower and therefore make it easier to maximize contact with the sorbent and are easier to remove/separate from the sorbent after the cleaning and/or rejuvenation process is complete, especially when heat is applied. Glycolipids are also water soluble, so a dilute solution can be used. Lipids with carbon atoms with a hydroxyl group are preferred as an optimum lipid for cleaning and rejuvenation of CZTS-Mixture. CZTS-Mixtures include, but are not limited to, coating granulated ferric oxide with CZTS or coating carbon-based sorbents with CZTS.

As an alternative to glycerin, some benefits for cleaning and/or rejuvenation of CZTS-Mixture can be realized using long chain alcohols (cetyl and stearyl alcohol) dissolved in hot water. However, glycerin is preferred over all other known cleaning and/or rejuvenation substances for CZTS-Mixture.

Captured contaminates such as mercury are soluble in simple lipids. Therefore, saturated CZTS-Mixture with contaminates can be sprayed in the cleaning and/or rejuvenation station 416 to extract and separate the contaminates from the CZTS-Mixture. After separating the simple lipids with the soluble contaminates from the CZTS-Mixture, a steam rinse and/or hot water rinse completes the process of the rejuvenation of CZTS-Mixture. The rinse can be pressurized rinse or a gravity flow rinse. This process completely cleans the CZTS-Mixture of all contaminates and rejuvenates it to original condition so that it can be returned to fluidized bed 152 through return port 420.

In accordance with this process, the simple lipids are heated to an optimal temperature of between 85 degrees Celsius (° C.) and 110 degrees Celsius (° C.). The heated simple lipids are then sprayed on the saturated CZTS-Mixture. Based on contact time, a lower effective temperature for heating the simple lipids of 5 degrees Celsius (° C.) above ambient and an upper effective temperature of 140 degrees Celsius (° C.) will work for the cleaning and/or rejuvenation of CZTS-Mixture.

An alternative process to the use of simple lipids to separate contaminates from CZTS-Mixture, which can be integrated into the cleaning and/or rejuvenation station 416, is the use of a vacuum dryer because mercury can be distilled and volatized. After contaminates are volatized in the vacuum dryer, the contaminates can be captured in filters and/or scrubbers. Scrubbers and filters can be especially effective when saturated in diluted simple lipids. Granulated ferric oxide coated with CZTS as a mixture is particularly efficient to extract phosphates from contaminated emissions and will volatize in a vacuum dryer.

Contaminated simple lipids which have been separated from CZTS-Mixture can be recycled after discharge from contaminant disposal port 418 in a process where contaminates are separated from the simple lipids by normal industry processes. After separation of contaminates, the spent simple lipids can be burned, while the contaminates are separately collected for recycling back into industry uses and/or proper disposal. If any CZTS-Mixture has been lost due to handling during the cleaning and/or rejuvenation process, bulk refill station 419 restores CZTS-Mixture to proper volumes in fluidized bed 152.

According to one exemplary embodiment of the subject disclosure, and as shown in FIG. 33, fluidized bed 152 can be a single unit with one or more sorbent recycling subsystems 400, 401, 402 configured for one or more sorbents. According to another exemplary embodiment (not shown), multiple fluidized beds 152 can be configured in series with each other, where each fluidized bed 152 is configured for one or more sorbent recycling subsystems 400, 401, 402. According to another exemplary embodiment (not shown), multiple fluidized beds 152 can be configured in parallel with each other, where each fluidized bed 152 is configured for one or more sorbent recycling subsystems 400, 401, 402.

Monitoring sensors 421, 422, 423, 424 are just a few non-exhaustive examples of measuring equipment that can be applied to the emissions control system. Those skilled in the art will appreciate that there may be many additional types of monitoring sensors located in many other stations of the emissions control system which have not been shown in the illustrated embodiments. The specific monitoring sensors used for gaseous contaminated emissions may be different than the specific monitoring sensors used for non-gaseous contaminated emissions. Similarly, the monitoring sensors required for one type of contaminant may be different than the monitoring sensors required for another contaminant.

In accordance with another aspect of the subject disclosure, an emissions control method is disclosed for removing contaminants from emissions. The method, which is illustrated in FIG. 33, includes the steps of routing the emissions into a treatment system including a reverse venturi shaped fluidized bed apparatus 152 containing one or more sorbents that chemically binds with contaminants carried in the emissions and routing the emissions away from the reverse venturi shaped fluidized bed apparatus 152 after the contaminants bind to the sorbents. In accordance with this method, the sorbent(s) is/are selected from a group of materials including: copper, zinc, tin, sulfur (CZTS) sorbents, copper, zinc, tin, sulfur (CZTS) alloy sorbents, and CZTS-Mixture sorbents. The method also includes the step of routing the sorbent through one or more sorbent recycling subsystems 400, 401, 402 for cleaning and rejuvenation. This step includes separating spent and exhausted sorbent from the sorbent routed through the sorbent recycling subsystem(s) 400, 401, 402, disposing of the spent and exhaust sorbent, separating contaminants from the sorbent routed through the sorbent recycling subsystem(s) 400, 401, 402, disposing of or recycling the contaminants, and returning the recycled sorbent to the reverse venturi shaped fluidized bed apparatus 152. Optionally, the method may include the step of routing new sorbent to the reverse venturi shaped fluidized bed apparatus 152 to replace the spent and exhaust sorbent.

In embodiments where the reverse venturi shaped fluidized bed apparatus 152 includes multiple sorbent recycling subsystems 400, 401, 402, the method may further include the steps of: maintaining different sorbents separate from one another in the reverse venturi shaped fluidized bed apparatus 152, detecting at least one process parameter of the reverse venturi shaped fluidized bed apparatus with one or more monitoring sensors 421, 422, 423, 424, routing the emissions through one or more of the different sorbents based on the at least one process parameter detected by the monitoring sensor(s) 421, 422, 423, 424, and then routing the different sorbents through different sorbent recycling subsystems 400, 401, 402 that are dedicated to processing a particular type of sorbent. For example, in the illustrated embodiment, copper, zinc, tin, sulfur (CZTS) sorbents are routed through first sorbent recycling subsystem 400, copper, zinc, tin, sulfur (CZTS) alloy sorbents are routed through second sorbent recycling subsystem 401, and copper, zinc, tin, sulfur (CZTS)-Mixture sorbents are routed through third sorbent recycling subsystem 402.

Extraction of Target Materials Using CZTS Sorbent.

Various embodiments of the present invention provide a method of extracting a target material from a medium. The method can include contacting a copper zinc tin sulfur (CZTS) sorbent with the target material in the medium including the target material. The contacting forms a used CZTS sorbent that includes the target material. Prior to the contacting, the CZTS sorbent can be substantially free of the target material or can include some target material. The used CZTS sorbent includes more of the target material than the CZTS sorbent prior to the contacting.

In some embodiments, the used CZTS is left in the medium and the method is free of separating the used CZTS from the medium. The method can include placing the medium including the used CZTS sorbent in a holding area, storage area, or settling area, such as a tank (e.g., a reaction tank or a settling tank), a holding pond, or sequestration area.

In some embodiments, the method includes separating the used CZTS sorbent from the medium. In some embodiments, the method also includes removing the target material from the used CZTS sorbent, to obtain an extract including the target material.

The method can include contacting the CZTS sorbent with the target material in any apparatus, such as the reverse venturi apparatus described herein, or such as any other suitable apparatus. The target material can be any suitable target material that can be at least partially removed from or sorbed out of a medium with the CZTS sorbent using the method described herein, including but not limited to any material described as a contaminant herein.

Target Material.

The target material can be any suitable target material. The method can remove one target material from the medium or more than one target material. The target material can include a gas, a liquid, a solid, a solute, or a combination thereof. The target material can include any material described herein as a contaminant, a metal, a heavy metal, a precious metal, a rare earth metal, a rare metal, an alkali metal, a transition metal, an alkaline earth metal, a metalloid, selenium, selenite, selenate, sulfur, nitrogen, nitrogen dioxide, nitrate, nitrite, phosphorus, phosphate, phosphite, sulfur, sulfur dioxide, ammonia, boron, a halogen, mercury, mercury oxide, a compound thereof, a complex thereof, a salt thereof, an organic solvent (e.g., a volatile organic solvent, such as benzene), or a combination thereof.

The target material can include a rare metal, such as tungsten, a compound thereof, or a combination thereof. The target material can include an alkali metal, such as lithium, a compound thereof, or a combination thereof. The target material can include a transition metal, such as manganese, zirconium, a compound thereof, or a combination thereof. The target material can include an alkaline earth metal, such as magnesium, a compound thereof, or a combination thereof. The target material can include a halogen, such as chlorine, iodine, bromide, fluoride, HCl, HI, HBr, HF, a chloride, an iodide, a bromide, a fluoride, or a combination thereof.

The target material can include a precious metal. The target material can include a coinage group metal, a platinum group metal, or a combination thereof. The target material can include gold, silver, a compound thereof, a complex thereof, a salt thereof, an oxide thereof, or a combination thereof. The target material can include gold, silver, or a combination thereof. The target material can include ruthenium, rhodium, palladium, osmium, iridium, platinum, a compound thereof, a complex thereof, a salt thereof, an oxide thereof, or a combination thereof. The target material can include ruthenium, rhodium, palladium, osmium, iridium, platinum, or a combination thereof.

The target material can include a rare earth metal. The target material can include cerium, dysprosium, erbium, europium, gadolinium, holmium, lanthanum, lutetium, neodymium, praseodymium, promethium, samarium, scandium, terbium, ytterbium, yttrium, thulium, a compound thereof, a complex thereof, a salt thereof, an oxide thereof, or a combination thereof. The target material can include cerium, dysprosium, erbium, europium, gadolinium, holmium, lanthanum, lutetium, neodymium, praseodymium, promethium, samarium, scandium, terbium, ytterbium, yttrium, or a combination thereof.

The target material can include a polluting substance, a toxic substance, a poisonous substance, or a combination thereof. The target material can include mercury, arsenic, barium, beryllium, cadmium, chromium, copper, lead, molybdenum, nickel, radium, selenium, a selenate, a selenite, thorium, uranium, vanadium, zinc, tin, a compound thereof, a complex thereof, a salt thereof, an oxide thereof, or a combination thereof. The target material can include mercury, an oxide thereof, a compound thereof, a salt thereof, or a combination thereof.

The method can be a method of removing phosphorus and/or phosphorus compounds from water. The medium can include water, and the target material can include phosphorus, phosphate, phosphite, a compound thereof, or a combination thereof. The method can include separating the used CZTS sorbent from the medium.

CZTS Sorbent.

The CZTS sorbent includes the elements copper, zinc, tin, and sulfur, which can be present in elemental form (e.g., as a mixture with one another), as one or more compounds including two or more of the elements (copper, zinc, tin, and sulfur), or a combination thereof. The CZTS sorbent can optionally include other elements, compounds thereof (e.g., compounds including only the other elements or also including copper, zinc, tin, and sulfur), or combinations thereof. The copper, zinc, tin, and sulfur can form the bulk or the CZTS sorbent, or can be present as a coating on another material to increase the surface area of combination of the copper, zinc, tin, and sulfur. Together the copper, zinc, tin, and sulfur can form any suitable proportion of the CZTS sorbent, such as 0.001 wt % to 100 wt % of the CZTS sorbent, 50 wt % to 100 wt %, or 0.001 wt % or more, or less than, equal to, or greater than 0.005 wt %, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or 99.999 wt %, or 100 wt % or less.

In some embodiments, the CZTS sorbent includes copper zinc tin sulfide having the formula Cu₂ZnSnS₄. Cu₂ZnSnS₄ is a I₂—II—IV-VI₄ quaternary compound that can have semiconducting properties. Cu₂ZnSnS₄ can have a kesterite structure. The Cu₂ZnSnS₄ can be present as an alloy, in an unalloyed form, or a combination thereof. The Cu₂ZnSnS₄ can form any suitable proportion of the CZTS sorbent, such as 0.001 wt % to 100 wt % of the CZTS sorbent, 50 wt % to 100 wt %, or 0.001 wt % or more, or less than, equal to, or greater than 0.005 wt %, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or 99.999 wt %, or 100 wt % or less.

In some embodiments, the CZTS sorbent includes ZnS, CuS, Cu₂SnS₃, CuZn₂, SnS, or a combination thereof; in other embodiments, the CZTS sorbent is substantially free of ZnS, CuS, Cu₂SnS₃, CuZn₂, SnS, or a combination thereof. The ZnS, CuS, Cu₂SnS₃, CuZn₂, SnS, or combination can be one or more phases within the CZTS, as a mixture within the CZTS, or a combination thereof. The ZnS, CuS, Cu₂SnS₃, CuZn₂, SnS, or combination thereof can be present with Cu₂ZnSnS₄, or the CZTS sorbent can be substantially free of Cu₂ZnSnS₄. The ZnS, CuS, Cu₂SnS₃, CuZn₂, SnS, or combination thereof can be any suitable proportion of the CZTS sorbent, such as 0.001 wt % to 100 wt % of the CZTS sorbent, 50 wt % to 100 wt %, or 0.001 wt % or more, or less than, equal to, or greater than 0.005 wt %, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or 99.999 wt %, or 100 wt % or less.

The CZTS sorbent can be substantially free of an element, metal, or compound in addition to copper, zinc, tin, and sulfur; in other embodiments, the CZTS sorbent can include an element, metal, or compound in addition to copper, zinc, tin, and sulfur. The element, metal, or compound in the CZTS sorbent can be included in the CZTS sorbent as a mixture, as an alloy, as a coating thereon, as a CZTS-coated material (e.g., such that coating of CZTS on the material increases the surface area of the material and uses the CZTS more efficiently in the method), or a combination thereof. The element, metal, or compound can include zinc, iron, aluminum, sulfur, selenium, a selenite, ferrous oxide, ferric oxide, or a combination thereof. The element, metal, or compound can include a clay, zeolite, a hydroxide salt, or a combination thereof. The element, metal, or compound can include bentonite, zeolite, calcium hydroxide, or a combination thereof. The element, metal, compound, or combination thereof can form any suitable proportion of the CZTS sorbent, such as 0.001 wt % to 99.999 wt % of the CZTS sorbent, 0.001 wt % to 70 wt %, 0.001 wt % to 20 wt %, or 0.001 wt % or more, or less than, equal to, or greater than 0.005 wt %, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, or 99.99 wt %, or 99.999 wt % or less.

The CZTS sorbent can have any suitable one or more physical forms when used for the removal of the target material from the medium. The CZTS sorbent can include particulate CZTS, monolithic CZTS, a CZTS coating, a CTZS sheet, a CTZS film, or a combination thereof.

The CZTS sorbent can have any suitable particle size, such as a volume-average particle size (e.g., 10%, 50%, 90%, or 100% volume-average particle size) of 0.5 nm to 3 inches, 0.5 nm to 7,500 microns, 0.5 nm or more, less than, equal to, or greater than 1 nm, 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 50, 100, 150, 200, 250, 400, 600, 800 nm, 1 micron, 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 150, 200, 250, 400, 600, 800 microns, 1 mm, 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75 mm, or 3 inches or less. The CZTS sorbent can have a 10% volume-average particle size of 0.01 microns to 1 micron, or 0.1 micron to 0.3 microns. The CZTS sorbent can have a 50% volume-average particle size of 1 micron to 20 microns, or 5 microns to 15 microns. The CZTS sorbent can have a 90% volume-average particle size of 10 microns to 40 microns, or 20 microns to 30 microns. The CZTS sorbent can have a 100% volume-average particle size of 20 microns to 60 microns, or 30 microns to 50 microns.

The CZTS sorbent can have any suitable surface area. The CZTS can have a surface area of 0.2 m²/g to 2000 m²/g, 1 m²/g to 30 m²/g, 10 m²/g to 15 m²/g, or 0.2 m²/g or more, or less than, equal to, or greater than 0.4 m²/g, 0.6, 0.8, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 24, 26, 28, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 150, 200, 500, 750, 1,000, 1,250, 1,500, 1,750 m²/g, or 2,000 m²/g or less.

The CZTS sorbent can have any suitable density. The CZTS sorbent can have a density of 2 to 8 g/cm³, or 4 to 5 g/cm³, or 4.5 to 4.6 g/cm³, or 2 g/cm³ or more, or less than, equal to, or greater than 2.2 g/cm³, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4, 5.6, 5.8, 6, 6.2, 6.4, 6.6, 6.8, 7, 7.2, 7.4, 7.6, or 7.8 g/cm³, or 8.0 g/cm³ or less.

Contacting the CZTS Sorbent with the Target Material.

The method includes contacting the CZTS sorbent with the target material in the medium including the target material. The method can include contacting the CZTS sorbent with the target material in any apparatus, such as the reverse venturi apparatus described herein, or such as any other suitable apparatus that provides removal of the target material from the medium by the sorbent. The contacting can include contacting the CZTS sorbent and the medium, such that the target material in the medium contacts the CZTS sorbent. The contacting of the CZTS sorbent and the target material can include flowing the medium through or by the CZTS sorbent, flowing the medium through a fixed or moving bed including the CZTS sorbent, flowing the medium through a column including the CZTS sorbent, flowing the medium through an apparatus including the CZTS sorbent deposited or placed therein, suspending the CZTS sorbent in the medium, injecting the CZTS sorbent into the medium, or a combination thereof. In some embodiments, the contacting includes flowing the medium through a reverse-venturi apparatus including the CZTS sorbent deposited therein.

The contacting can be performed at any suitable temperature. The contacting can be performed at ambient temperature. The contacting can be performed at a temperature of −100° C. to 5,000° C., 1° C. to 300° C., or −100° C. or more, or less than, equal to, or greater than −90° C., −80, −70, −60, −50, −40, −30, −20, −10, −5, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 140, 150, 175, 200, 250, 500, 1,000, 1,500, 2,000, or 2,500° C., or 5,000° C. or less.

The contacting can be performed for any suitable duration. The contacting can including a continuous process, such as including flowing the medium including the target material by the CZTS sorbent at any suitable flow rate. The contacting can include a batch-type process, such as allowing the medium including the target material to sit in contact with the CZTS sorbent for a suitable period of time. The contacting can be performed with or without agitation of the medium to ensure adequate and effective contact with the CZTS sorbent. The contacting between the CZTS sorbent and the target material in the medium can be performed for a duration of 30 d to 0.000001 s, 1 h to 0.000001 s, or 30 d or less, or less than, equal to, or greater than 25 d, 20, 15, 10, 5, 1 d, 20 h, 16, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1.5, 1 h, 50 min, 40, 30, 25, 20, 15, 10, 5, 4, 3, 2, 1 min, 50 s, 40, 30, 25, 20, 15, 10, 5, 4, 3, 2, 1 s, 0.1, 0.01, 0.001, 0.0001, or 0.00001 s, or 0.000001 s or more.

The medium can be any suitable material that includes the target material. The medium can include a liquid, gas, solid, or a combination thereof. The medium can include water, an organic solvent, a non-organic solvent, an oil, sulfur, sulfuric acid, sulfur, a surfactant, a detergent, chlorine, iodine, bromide, fluoride, HCl, HI, HBr, HF, a chloride, an iodide, a bromide, a fluoride, or a combination thereof. The medium can be an aqueous medium or an organic medium. The aqueous medium can include any suitable proportion of water, such as 50 wt % to 100 wt % of the aqueous medium, 80 wt % to 100 wt %, 50 wt % or more, or less than, equal to, or greater than 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, 99.999 wt %, or 100 wt % or less.

The medium can include a medium from a combustion process in a power plant, such as a coal-fired power plant or a natural gas power plant, such as any medium that includes combustion products from the combustion process. The medium can include solid, liquid, and/or gaseous effluent from a combustion process or cleanup process (e.g., a process that removes a polluting substance, a toxic substance, a poisonous substance, or a combination thereof), such as from a power plant, such as from a coal-fired electrical plant or a natural gas power plant. The medium can include flue gas from a combustion process in a natural gas power plant. The medium can include flue gas from a combustion process in a coal-fired electrical plant, water from the coal-fired electrical plant (e.g., used for scrubbing the flue gas), discharge from the coal-fired electrical place, runoff from the coal-fired electrical plant, leachate from the coal-fired electrical plant, a stream to and/or from ash ponds, a stream to and/or from a mining operation, a stream to and/or from a coal-mining operation, or a combination thereof.

The medium can include a medium used in or obtain from a mining operation, such as a solid and/or liquid used in or obtained from a mining operation. The medium from a mining operation in some examples can be an aqueous medium. In some embodiments, the mining operation is a mining operation to mine the target material; in other embodiments, another one or more materials other than the target material is the objective of the mining operation and removal of the target material is ancillary to the primary target of the mining operation (e.g., wherein the primary target can refer to the largest volume target, the target that generates the greatest profit, or a combination thereof).

The target material can form any suitable proportion of the medium. The target material can be 1 part per trillion to 99.999 wt % of the medium, 0.001 wt % to 20 wt % of the medium, or 1 part per trillion or more, 10 parts per trillion, 20, 25, 50, 75, 100, 150, 200, 250, 500, 750 parts per trillion, 1 part per billion, 10 parts per billion, 20, 25, 50, 75, 100, 150, 200, 250, 500, 750 parts per billion, 1 part per million, 10 parts per million, 20, 25, 50, 75, 100, 150, 200, 250, 500, 750 parts per million, 0.001 wt %, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or 99.999 wt %, or 100 wt % or less.

Used CZTS Sorbent.

The used CZTS sorbent includes the target material. The used CZTS sorbent includes a greater concentration of the target material than the CZTS prior to contacting with the target material, wherein the CZTS prior to contacting the target material can either include some target material or can be substantially free of the target material. The used CZTS sorbent can include the target material in any suitable form on or in the used CZTS sorbent such as on and/or in the CZTS sorbent, absorbed on and/or in the CZTS sorbent, adsorbed and/or in the CZTS sorbent, complexed on and/or in the CZTS sorbent, amalgamed on and/or in the CZTS sorbent, or a combination thereof. The used CZTS sorbent can include the target material in an unchanged chemical state as compared to the form of the target material in the medium, as a complex, compound, or amalgam formed with the CZTS sorbent (e.g., as an amalgam with materials in the CZTS sorbent, such as with Cu₂ZnSnS₄, ZnS, CuS, Cu₂SnS₃, CuZn₂, SnS, or a combination thereof), or a combination thereof.

The target material can be any suitable proportion of the used CZTS sorbent. The target material can be 1 part per trillion to 50 wt % of the used CZTS sorbent, 0.0001 wt % to 20 wt %, or 1 part per trillion or more, 10 parts per trillion, 20, 25, 50, 75, 100, 150, 200, 250, 500, 750 parts per trillion, 1 part per billion, 10 parts per billion, 20, 25, 50, 75, 100, 150, 200, 250, 500, 750 parts per billion, 1 part per million, 10 parts per million, 20, 25, 50, 75, 100, 150, 200, 250, 500, 750 parts per million, 0.001 wt %, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, or 45 wt %, or 50 wt % or less.

In some embodiments, the used CZTS can be stored for long periods or indefinitely as a method of sequestering the target material from the environment. For example, the used CZTS can be placed in a holding pond, in a storage container, or can be incorporated with other materials (e.g., cement) for long-term storage or sequestration.

Separating the Used CZTS Sorbent from the Medium.

The method can include separating the used CZTS sorbent from the medium. The separating can be performed in any suitable way that removes the used CZTS sorbent from the bulk of the medium. The separating can include removing the used CZTS sorbent from the medium, removing the medium from the used CZTS sorbent, or a combination thereof.

The removal of the used CZTS sorbent from the medium can occur by flowing the medium by the CZTS sorbent, such that the medium previously contacted with the CZTS sorbent has flowed by the CZTS sorbent such that the used CZTS sorbent is no longer in contact with the medium previously contacted with the CZTS sorbent. As such, the removal can occur naturally as a property of the contacting process; for example, the removing can include flowing the medium through a fixed bed including the CZTS sorbent, flowing the medium through a column including the CZTS sorbent, flowing the medium through an apparatus including the CZTS sorbent deposited therein, or a combination thereof. The removing can include removing the medium from a suspension of the CZTS sorbent in the medium. The removing can include removing CZTS sorbent from a medium into which the CZTS sorbent was placed or injected. The separating can include separating the used CZTS sorbent from the medium using a particulate separation device, such as a filter, an electrostatic precipitator, a scrubber, or a combination thereof. The separating can include filtering the used CZTS sorbent from the medium. In some embodiments, the separating can include replacing the medium including the target material with a different medium, such as another medium including the target material, a medium including less of the target material, or a medium that is substantially free of the target material. The separating can include rinsing the used CZTS sorbent, such as with an organic medium, an aqueous medium, or a combination thereof.

Any suitable proportion of the medium that is separated from the used CZTS sorbent can be the target material. The medium that is separated from the used CZTS sorbent can have a lower concentration of the target material than the medium including the target material prior to contacting with the CZTS sorbent. The target material can be 0 wt % to 99.99 wt % of the medium having the CZTS sorbent separated therefrom, 0 wt % to 20 wt %, 0 wt % to 5 wt %, 0 wt % to 0.1 wt %, or 0 wt % or more, or less than, equal to, or greater than 0.01, 0.02, 0.04, 0.06, 0.08, 0.1, 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9 wt %, or 99.99 wt % or less. In some embodiments, the medium having the CZTS sorbent separated therefrom is substantially free of the target material.

Removing the Target Material from the Used CZTS Sorbent, to Obtain an Extract Including the Target Material.

In various embodiments, the method can include removing the target material from the used CZTS sorbent. Removal of the target material from the used CZTS sorbent provides an extract that includes the target material. The extract can be enriched in the target material relative to the medium that included the target material prior to contacting with the CZTS sorbent. The extract can include a greater concentration of the target material than a concentration of the target material in the medium prior to contacting with the CZTS sorbent. The target material can be any suitable proportion of the extract, such as 1 part per trillion to 100 wt % of the extract, 0.001 wt % to 99.9 wt % of the extract, or 1 part per trillion or more, 10 parts per trillion, 20, 25, 50, 75, 100, 150, 200, 250, 500, 750 parts per trillion, 1 part per billion, 10 parts per billion, 20, 25, 50, 75, 100, 150, 200, 250, 500, 750 parts per billion, 1 part per million, 10 parts per million, 20, 25, 50, 75, 100, 150, 200, 250, 500, 750 parts per million, 0.001 wt %, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 82, 84, 86, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, 99.99, or 99.999 wt %, or 100 wt % or less.

The extract can include a liquid or gas used for the removing of the target material from the used CTZS sorbent, a derivative of a liquid or gas used for the removing of the target material from the used CTZS sorbent, or a combination thereof. The extract can be substantially free of the CZTS sorbent, or can include some CZTS sorbent (e.g., less of the CZTS sorbent than was present in the used CZTS sorbent). The extract can be substantially free of Cu₂ZnSnS₄, ZnS, CuS, Cu₂SnS₃, CuZn₂, SnS, or a combination thereof, or the extract can include one or more of these materials. The extract can be substantially free of the medium, or the extract can include some of the medium.

The removing of the target material from the medium can be performed in any suitable way that generates the extract. The removing can include heating the used CZTS sorbent, extracting the target material from the used CZTS sorbent using liquid or gaseous extraction, dissolving the CZTS from the used CZTS sorbent (e.g., via reaction with one or more acids or other materials), chemically-reacting the target material in the CZTS sorbent, chemically-reacting the CZTS in the used CZTS sorbent, or a combination thereof. The removing can include placing the used CZTS sorbent in a vacuum drier. The removing can include rinsing the used CZTS sorbent with an aqueous medium, an organic medium, or a combination thereof. The removing can include rinsing the used CZTS sorbent with water or steam.

The removing can include contacting the used CZTS sorbent with a chemical reagent including an organic solvent, a fatty alcohol, a lipid, a glycolipid, or a combination thereof, optionally as a mixture with water. The chemical reagent can include methanol, methyl ethyl ketone, methylene chlorine, glycerin, cetyl alcohol, stearyl alcohol, or a combination thereof, optionally as a mixture with water. The contacting of the used CZTS sorbent with the chemical reagent can be conducted under any suitable pH conditions, such as at a pH of 1 to 20, 6.49 to 9.05, or 1 or more, or less than, equal to, or greater than 2, 3, 4, 5, 5.5, 6, 6.1, 6.2, 6.4, 6.6, 6.8, 7, 7.2, 7.4, 7.6, 7.8, 8, 8.2, 8.4, 8.6, 8.8, 9, 9.2, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19, or 20 or less. The contacting of the used CZTS sorbent with the chemical reagent can be performed at any suitable temperature, such as 5 to 140° C., 85 to 110° C., or 5° C. or more, or 10° C., 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135° C., or 140° C. or less.

The removal of the target material from the used CZTS sorbent can provide a recovered or regenerated CTZS sorbent. In some embodiments, the recovered or regenerated CTZS sorbent can be disposed of or otherwise used without reuse in the method of extracting target materials with the CTZS sorbent. In some embodiments, the method includes reusing the recovered or regenerated CTZS sorbent one or more times in the method. The method can include processing the recovered CZTS sorbent such that the recovered CZTS sorbent is effective for reuse in the method as the CTZS sorbent (e.g., regenerated); in some embodiments, removing the target material from the used CZTS is the only processing needed to prepare the sorbent for reuse (e.g., the recovered CZTS is a regenerated CTZS sorbent), while in other embodiments further processing steps are included to prepare the recovered CZTS sorbent for reuse and regenerate the sorbent.

Method of Forming a CZTS Sorbent.

In various embodiments, the present invention provides a method of forming the CTZS sorbent describes herein. The method can include combining copper, zinc, tin, and sulfur starting materials, in their elemental form, as compounds (e.g., compounds of one another, including other materials, or a combination thereof), as salts (e.g., salts of one another, including other materials, or a combination thereof), or a combination thereof, under conditions suitable to provide the CTZS sorbent. The method can include mixing the starting materials, such as before heating, during heating, or a combination thereof.

In some embodiments, the method includes combining a copper salt (e.g., copper acetate dihydrate), a zinc salt (e.g., zinc acetate dihydrate), a tin salt (e.g., tin chloride dihydrate), and a sulfur compound (e.g., thiourea) in proportions suitable for and under conditions suitable for forming the CTZS sorbent.

The copper, zinc, tin, and sulfur in the mixture of starting material can independently form any suitable proportion of the starting material mixture, such that a CTZS sorbent that can be used in the method of extraction of target materials is formed. The copper in the mixture of starting materials can be 20 wt % to 30 wt %, 24 wt to 26 wt %, 24.5 wt % to 25.5 wt %, or about 24.92 wt % of the total copper, zinc, tin, and sulfur present in the starting material mixture. The zinc in the mixture of starting materials can be 10 wt % to 25 wt %, 15 wt % to 20 wt %, 17 wt % to 19 wt %, 17.5 wt % to 18.5 wt %, or about 18.10 wt % of the total copper, zinc, tin, and sulfur present in the starting material mixture. The tin in the mixture of starting materials can be 20 wt % to 35 wt %, 25 wt % to 30 wt %, 26 wt % to 28 wt %, 26.5 wt % to 28 wt %, or about 27.39 wt % of the total copper, zinc, tin, and sulfur present in the starting material mixture. The sulfur in the mixture of starting materials can be 25 wt % to 30 wt %, 28 wt % to 32 wt %, 29 wt % to 30 wt %, or about 29.59 wt % of the total copper, zinc, tin, and sulfur present in the starting material mixture.

The method can include heating the starting materials. The heating can be performed for any suitable duration, such as 1 min to 24 h, 20 min to 4 h, or 1 min or more, or less than, equal to, or greater than 2 min, 4, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 min, 1 h, 1.5, 2, 2.5, 3, 3.5, 4, 5, 6, 8, 10, 12, 14, 16, 18, 20, 22 h, or 24 h or less. The heating can include heating to any suitable temperature, such as 50° C. to 1,000° C., 75° C. to 300° C., or 50° C. or more, or less than, equal to, or greater than 60° C., 70, 80, 90, 100, 110, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 500, 600, 700, 800, or 900° C., or 1,000° C. or less. The method can include grinding or otherwise physically processing the reaction product to provide CTZS sorbent having the desired particle size.

The method of forming the CZTS sorbent can include adding one or more additional materials to the copper, zinc, tin, and sulfur starting materials. The method can include adding water to the starting materials prior to the heating, during the heating, or a combination thereof.

It should be appreciated that although the steps of the methods are described and illustrated herein in a particular order, the steps may be performed in a different order without departing from the scope of the subject disclosure, except where the order of the steps is otherwise noted. In the same vein, it should be appreciated that the methods described and illustrated herein may be performed without the inclusion of all the steps described above or with the addition of intervening steps that have not been discussed, all without departing from the scope of the subject disclosure.

Many modifications and variations of the present disclosure are possible in light of the above teachings and may be practiced otherwise than as specifically described while within the scope of the appended claims.

Exemplary Embodiments

The following exemplary embodiments are provided, the numbering of which is not to be construed as designating levels of importance:

Embodiment 1 provides a method of extracting a target material from a medium, the method comprising:

contacting a copper zinc tin sulfur (CZTS) sorbent with the target material in the medium comprising the target material to form a used CZTS sorbent that comprises the target material.

Embodiment 2 provides the method of Embodiment 1, wherein the method further comprises placing the medium comprising the used CZTS sorbent in a holding area, storage area, settling area, and/or sequestration area.

Embodiment 3 provides the method of any one of Embodiments 1-2, wherein the method further comprises placing the medium comprising the used CZTS sorbent in a sequestration area, a holding pond, a reaction tank, or a settling tank.

Embodiment 4 provides the method of any one of Embodiments 1-3, wherein the method further comprises separating the used CZTS sorbent from the medium.

Embodiment 5 provides the method of Embodiment 4, further comprising removing the target material from the used CZTS sorbent, to obtain an extract comprising the target material.

Embodiment 6 provides the method of any one of Embodiments 1-5, wherein the target material comprises a metal, a heavy metal, a precious metal, a rare earth metal, a rare metal, an alkali metal, a transition metal, an alkaline earth metal, a metalloid, selenium, selenite, selenate, sulfur, nitrogen, nitrogen dioxide, nitrate, nitrite, phosphorus, phosphate, phosphite, sulfur, sulfur dioxide, ammonia, boron, a halogen, mercury, mercury oxide, a compound thereof, a complex thereof, a salt thereof, an organic solvent, or a combination thereof.

Embodiment 7 provides the method of any one of Embodiments 1-6, wherein the target material comprises a rare metal.

Embodiment 8 provides the method of Embodiment 7, wherein the target material comprises tungsten, a compound thereof, or a combination thereof.

Embodiment 9 provides the method of any one of Embodiments 1-8, wherein the target material comprises an alkali metal.

Embodiment 10 provides the method of Embodiment 9, wherein the target material comprises lithium, a compound thereof, or a combination thereof.

Embodiment 11 provides the method of any one of Embodiments 1-10, wherein the target material comprises a transition metal.

Embodiment 12 provides the method of Embodiment 11, wherein the target material comprises manganese, zirconium, a compound thereof, or a combination thereof.

Embodiment 13 provides the method of any one of Embodiments 1-12, wherein the target material comprises an alkaline earth metal.

Embodiment 14 provides the method of Embodiment 13, wherein the target material comprises magnesium, a compound thereof, or a combination thereof.

Embodiment 15 provides the method of any one of Embodiments 1-14, wherein the target material comprises a halogen.

Embodiment 16 provides the method of any one of Embodiments 1-15, wherein the target material comprises chlorine, iodine, bromide, fluoride, HCl, HI, HBr, HF, a chloride, an iodide, a bromide, a fluoride, or a combination thereof.

Embodiment 17 provides the method of any one of Embodiments 1-16, wherein the target material comprises a precious metal.

Embodiment 18 provides the method of any one of Embodiments 1-17, wherein the target material comprises a coinage group metal, a platinum group metal, or a combination thereof.

Embodiment 19 provides the method of any one of Embodiments 1-18, wherein the target material comprises gold, silver, a compound thereof, a complex thereof, a salt thereof, an oxide thereof, or a combination thereof.

Embodiment 20 provides the method of any one of Embodiments 1-19, wherein the target material comprises gold, silver, or a combination thereof.

Embodiment 21 provides the method of any one of Embodiments 1-20, wherein the target material comprises ruthenium, rhodium, palladium, osmium, iridium, platinum, a compound thereof, a complex thereof, a salt thereof, an oxide thereof, or a combination thereof.

Embodiment 22 provides the method of any one of Embodiments 1-21, wherein the target material comprises ruthenium, rhodium, palladium, osmium, iridium, platinum, or a combination thereof.

Embodiment 23 provides the method of any one of Embodiments 1-22, wherein the target material comprises a rare earth metal.

Embodiment 24 provides the method of any one of Embodiments 1-23, wherein the target material comprises cerium, dysprosium, erbium, europium, gadolinium, holmium, lanthanum, lutetium, neodymium, praseodymium, promethium, samarium, scandium, terbium, ytterbium, yttrium, thulium, a compound thereof, a complex thereof, a salt thereof, an oxide thereof, or a combination thereof.

Embodiment 25 provides the method of any one of Embodiments 1-24, wherein the target material comprises cerium, dysprosium, erbium, europium, gadolinium, holmium, lanthanum, lutetium, neodymium, praseodymium, promethium, samarium, scandium, terbium, ytterbium, yttrium, or a combination thereof.

Embodiment 26 provides the method of any one of Embodiments 1-25, wherein the target material comprises a polluting substance, a toxic substance, a poisonous substance, or a combination thereof.

Embodiment 27 provides the method of any one of Embodiments 1-26, wherein the target material is mercury, arsenic, barium, beryllium, cadmium, chromium, copper, lead, molybdenum, nickel, radium, selenium, a selenate, a selenite, thorium, uranium, vanadium, zinc, tin, a compound thereof, a complex thereof, a salt thereof, an oxide thereof, or a combination thereof.

Embodiment 28 provides the method of any one of Embodiments 1-27, wherein the target material is mercury, an oxide thereof, a compound thereof, a salt thereof, or a combination thereof.

Embodiment 29 provides the method of any one of Embodiments 1-28, wherein the target material is a gas, a liquid, a solid, a solute, or a combination thereof.

Embodiment 30 provides the method of any one of Embodiments 1-29, wherein the target material is 1 part per trillion to 99.999 wt % of the medium.

Embodiment 31 provides the method of any one of Embodiments 1-30, wherein the target material is 0.001 wt % to 20 wt % of the medium.

Embodiment 32 provides the method of any one of Embodiments 1-31, wherein the medium comprises liquid, gas, solid, or a combination thereof.

Embodiment 33 provides the method of any one of Embodiments 1-32, wherein the medium comprises water, an organic solvent, an oil, or a combination thereof.

Embodiment 34 provides the method of any one of Embodiments 1-33, wherein the medium is an aqueous medium.

Embodiment 35 provides the method of Embodiment 34, wherein water is 50 wt % to 100 wt % of the aqueous medium.

Embodiment 36 provides the method of any one of Embodiments 34-35, wherein water is 80 wt % to 100 wt % of the aqueous medium.

Embodiment 37 provides the method of any one of Embodiments 1-36, wherein the medium comprises solid, liquid, and/or gaseous effluent from a combustion process or cleanup process in a power plant.

Embodiment 38 provides the method of any one of Embodiments 1-37, wherein the medium is a medium from a combustion or cleanup process in a coal-fired power plant.

Embodiment 39 provides the method of any one of Embodiments 1-38, wherein the medium is a medium from a combustion process in a natural gas power plant.

Embodiment 40 provides the method of any one of Embodiments 1-39, wherein the medium comprises flue gas from a coal-fired electrical plant, water from the coal-fired electrical plant, discharge from the coal-fired electrical place, runoff from the coal-fired electrical plant, leachate from the coal-fired electrical plant, a stream to and/or from ash ponds, a stream to and/or from a mining operation, a stream to and/or from a coal-mining operation, or a combination thereof.

Embodiment 41 provides the method of any one of Embodiments 1-40, wherein the medium comprises a solid, liquid, and/or gaseous effluent from a combustion process in a power plant.

Embodiment 42 provides the method of any one of Embodiments 1-41, wherein the medium comprises a solid and/or liquid used in or obtained from a mining operation.

Embodiment 43 provides the method of any one of Embodiments 1-42, wherein the medium is a solid medium.

Embodiment 44 provides the method of any one of Embodiments 1-43, wherein the medium comprises a non-organic solvent.

Embodiment 45 provides the method of any one of Embodiments 1-44, wherein the medium comprises sulfuric acid, sulfur, a surfactant, a detergent, or a combination thereof.

Embodiment 46 provides the method of any one of Embodiments 1-45, wherein the medium comprises a chloride, bromide, fluoride, or a combination thereof.

Embodiment 47 provides the method of any one of Embodiments 1-46, wherein the target material is 1 part per trillion to 50 wt % of the used CZTS sorbent.

Embodiment 48 provides the method of any one of Embodiments 1-47, wherein the target material is 0.0001 wt % to 20 wt % of the used CZTS sorbent.

Embodiment 49 provides the method of any one of Embodiments 1-48, wherein the used CZTS sorbent comprises the target material on and/or in the CZTS sorbent, the target material absorbed on and/or in the CZTS sorbent, adsorbed and/or in the CZTS sorbent, complexed on and/or in the CZTS sorbent, amalgamed on and/or in the CZTS sorbent, or a combination thereof.

Embodiment 50 provides the method of any one of Embodiments 1-49, wherein the used CZTS sorbent comprises the target material in an unchanged chemical state as compared to the form of the target material in the medium, as a complex, compound, or amalgam formed with the CZTS sorbent, or a combination thereof.

Embodiment 51 provides the method of any one of Embodiments 1-50, wherein the used CZTS sorbent comprises the target material as an amalgam formed with the CZTS sorbent.

Embodiment 52 provides the method of any one of Embodiments 5-51, wherein the target material is 1 part per trillion to 100 wt % of the extract.

Embodiment 53 provides the method of any one of Embodiments 5-52, wherein the target material is 0.001 wt % to 99.9 wt % of the extract.

Embodiment 54 provides the method of any one of Embodiments 5-53, wherein the extract comprises a liquid or gas used for the removing of the target material from the used CTZS sorbent, a derivative of a liquid or gas used for the removing of the target material from the used CTZS sorbent, or a combination thereof.

Embodiment 55 provides the method of any one of Embodiments 5-54, wherein the extract is substantially free of the CZTS sorbent and CZTS.

Embodiment 56 provides the method of any one of Embodiments 5-55, wherein the extract is substantially free of the medium.

Embodiment 57 provides the method of any one of Embodiments 1-56, wherein CZTS sorbent comprises a mixture comprising copper, zinc, tin, and sulfur.

Embodiment 58 provides the method of any one of Embodiments 1-57, wherein the CZTS sorbent comprises copper zinc tin sulfide having the formula Cu₂ZnSnS₄.

Embodiment 59 provides the method of any one of Embodiments 1-58, wherein the CZTS comprises ZnS, CuS, Cu₂SnS₃, CuZn₂, SnS, or a combination thereof.

Embodiment 60 provides the method of any one of Embodiments 1-59, wherein CZTS is 0.001 wt % to 100 wt % of the CZTS sorbent.

Embodiment 61 provides the method of any one of Embodiments 1-60, wherein CZTS is 50 wt % to 100 wt % of the CZTS sorbent.

Embodiment 62 provides the method of any one of Embodiments 1-61, wherein the CZTS in the CZTS sorbent is unalloyed CZTS, an alloy of CZTS, or a combination thereof.

Embodiment 63 provides the method of any one of Embodiments 1-62, wherein the CZTS sorbent comprises an element, metal, or compound in addition to copper, zinc, tin, and sulfur.

Embodiment 64 provides the method of Embodiment 63, wherein the element, metal, or compound in the CZTS sorbent is comprised in the CZTS sorbent as a mixture, as an alloy, as a coating thereon, as a CZTS-coated material, or a combination thereof.

Embodiment 65 provides the method of any one of Embodiments 63-64, wherein the element, metal, or compound in the CZTS sorbent comprises zinc, iron, aluminum, sulfur, selenium, a selenite, ferrous oxide, ferric oxide, or a combination thereof.

Embodiment 66 provides the method of any one of Embodiments 63-65, wherein the element, metal, or compound in the CZTS sorbent comprises a clay, zeolite, a hydroxide salt, or a combination thereof.

Embodiment 67 provides the method of any one of Embodiments 63-66, wherein the element, metal, or compound in the CZTS sorbent comprises bentonite, zeolite, calcium hydroxide, or a combination thereof.

Embodiment 68 provides the method of any one of Embodiments 63-67, wherein the element, metal, or compound in the CZTS sorbent is 0.001 wt % to 70 wt % of the CZTS sorbent.

Embodiment 69 provides the method of any one of Embodiments 1-68, wherein the CZTS sorbent comprises particulate CZTS, monolithic CZTS, a CZTS coating, a CTZS sheet, a CTZS film, or a combination thereof.

Embodiment 70 provides the method of any one of Embodiments 1-69, wherein the CZTS sorbent has a particle size of 0.5 nm to 3 inches.

Embodiment 71 provides the method of any one of Embodiments 1-70, wherein the CZTS sorbent has a particle size of 0.5 nm to 7,500 microns.

Embodiment 72 provides the method of any one of Embodiments 1-71, wherein the CZTS sorbent has a surface area of 0.2 m²/g to 2000 m²/g.

Embodiment 73 provides the method of any one of Embodiments 1-72, wherein the CZTS sorbent has a density of 2 to 8 g/cm³.

Embodiment 74 provides the method of any one of Embodiments 1-73, wherein the CZTS sorbent has a density of 4 to 5 g/cm³.

Embodiment 75 provides the method of any one of Embodiments 1-74, wherein the CZTS sorbent has a density of 4.5 to 4.6 g/cm³.

Embodiment 76 provides the method of any one of Embodiments 1-75, wherein the contacting comprises contacting the CZTS sorbent and the medium.

Embodiment 77 provides the method of any one of Embodiments 1-76, wherein the contacting comprises flowing the medium through or by the CZTS sorbent, flowing the medium through a fixed or moving bed comprising the CZTS sorbent, flowing the medium through a column comprising the CZTS sorbent, flowing the medium through an apparatus comprising the CZTS sorbent deposited or placed therein, suspending the CZTS sorbent in the medium, injecting the CZTS sorbent into the medium, or a combination thereof.

Embodiment 78 provides the method of any one of Embodiments 1-77, wherein the contacting comprises flowing the medium through a reverse-venturi apparatus comprising the CZTS sorbent deposited therein.

Embodiment 79 provides the method of any one of Embodiments 1-78, wherein the contacting is performed at ambient temperature.

Embodiment 80 provides the method of any one of Embodiments 1-79, wherein the contacting is performed at a temperature of −100° C. to 5,000° C.

Embodiment 81 provides the method of any one of Embodiments 1-80, wherein the contacting is performed at a temperature of 1° C. to 300° C.

Embodiment 82 provides the method of any one of Embodiments 1-81, wherein the contacting is performed for a duration of 30 d to 0.000001 s.

Embodiment 83 provides the method of any one of Embodiments 1-82, wherein the contacting is performed for a duration of 1 h to 0.000001 s.

Embodiment 84 provides the method of any one of Embodiments 4-83, wherein the separating comprises removing the used CZTS sorbent from the medium, removing the medium from the used CZTS sorbent, or a combination thereof.

Embodiment 85 provides the method of any one of Embodiments 4-84, wherein the separating comprises separating the used CZTS sorbent from the medium using a particulate separation device.

Embodiment 86 provides the method of Embodiment 85, wherein the particulate separation device comprises a filter, an electrostatic precipitator, a scrubber, or a combination thereof.

Embodiment 87 provides the method of any one of Embodiments 4-86, wherein the separating comprises filtering the used CZTS sorbent from the medium.

Embodiment 88 provides the method of any one of Embodiments 4-87, wherein the separating comprises replacing the medium comprising the target material with a different medium.

Embodiment 89 provides the method of any one of Embodiments 4-88, wherein the target material is about 0 wt % to 99.99 wt % of the medium having the CZTS sorbent separated therefrom.

Embodiment 90 provides the method of any one of Embodiments 4-89, wherein the target material is about 0 wt % to 20 wt % of the medium having the CZTS sorbent separated therefrom.

Embodiment 91 provides the method of any one of Embodiments 4-90, wherein the target material is 0 wt % to 5 wt % of the medium having the CZTS sorbent separated therefrom.

Embodiment 92 provides the method of any one of Embodiments 4-91, wherein the target material is about 0 wt % to 0.1 wt % of the medium having the CZTS sorbent separated therefrom.

Embodiment 93 provides the method of any one of Embodiments 4-92, wherein the medium having the CZTS sorbent separated therefrom is substantially free of the target material.

Embodiment 94 provides the method of any one of Embodiments 5-93, wherein the extract comprises a greater concentration of the target material than a concentration of the target material in the medium.

Embodiment 95 provides the method of any one of Embodiments 5-94, wherein the removing comprises heating the used CZTS sorbent, extracting the target material from the used CZTS sorbent using liquid or gaseous extraction, dissolving the CZTS from the used CZTS sorbent, chemically-reacting the target material in the CZTS sorbent, chemically-reacting the CZTS in the used CZTS sorbent, or a combination thereof.

Embodiment 96 provides the method of any one of Embodiments 5-95, wherein the removing comprises placing the used CZTS sorbent in a vacuum drier.

Embodiment 97 provides the method of any one of Embodiments 5-96, wherein the removing comprises contacting the used CZTS sorbent with a chemical reagent comprising an organic solvent, a fatty alcohol, a lipid, a glycolipid, or a combination thereof, optionally as a mixture with water.

Embodiment 98 provides the method of Embodiment 97, wherein the chemical reagent comprises methanol, methyl ethyl ketone, methylene chlorine, glycerin, cetyl alcohol, stearyl alcohol, or a combination thereof, optionally as a mixture with water.

Embodiment 99 provides the method of any one of Embodiments 97-98, wherein the contacting of the used CZTS sorbent with the chemical reagent is conducted at a pH of 6.49-9.05.

Embodiment 100 provides the method of any one of Embodiments 97-99, wherein the contacting of the used CZTS sorbent with the chemical reagent is performed at 5 to 140° C.

Embodiment 101 provides the method of any one of Embodiments 97-100, wherein the contacting of the used CZTS sorbent with the chemical reagent is performed at 85 to 110° C.

Embodiment 102 provides the method of any one of Embodiments 97-101, wherein the removing further comprises rinsing the used CZTS sorbent with water or steam.

Embodiment 103 provides the method of any one of Embodiments 5-102, wherein the removing provides a recovered or regenerated CTZS sorbent.

Embodiment 104 provides the method of Embodiment 103, further comprising processing the recovered CZTS sorbent such that the recovered CZTS sorbent is a regenerated CTZS sorbent effective for reuse in the method as the CTZS sorbent.

Embodiment 105 provides the method of any one of Embodiments 103-104, further comprising reusing the recovered or regenerated CTZS sorbent in the method as the CTZS sorbent.

Embodiment 106 provides the method of any one of Embodiments 1-105, wherein the method is a method of removing phosphorus and/or phosphorus compounds from water, wherein the medium comprises water, wherein the target material comprises phosphorus, phosphate, phosphite, a compound thereof, or a combination thereof, wherein the method further comprises separating the used CZTS sorbent from the medium.

Embodiment 107 provides a method of extracting a target material from a medium, the method comprising:

contacting a copper zinc tin sulfur (CZTS) sorbent with the target material in the medium comprising the target material to form a used CZTS sorbent that comprises the target material, wherein the target material comprises a metal, a heavy metal, a precious metal, a rare earth metal, a rare metal, an alkali metal, a transition metal, an alkaline earth metal, a metalloid, selenium, selenite, selenate, sulfur, nitrogen, nitrogen dioxide, nitrate, nitrite, phosphorus, phosphate, phosphite, sulfur, sulfur dioxide, ammonia, boron, a halogen, mercury, mercury oxide, a compound thereof, a complex thereof, a salt thereof, an organic solvent, or a combination thereof.

Embodiment 108 provides a method of extracting a target material from a medium, the method comprising:

contacting a copper zinc tin sulfur (CZTS) sorbent with the target material in the medium comprising the target material to form a used CZTS sorbent that comprises the target material, wherein the target material comprises a metal, a heavy metal, a precious metal, a rare earth metal, a rare metal, an alkali metal, a transition metal, an alkaline earth metal, a metalloid, selenium, selenite, selenate, sulfur, nitrogen, nitrogen dioxide, nitrate, nitrite, phosphorus, phosphate, phosphite, sulfur, sulfur dioxide, ammonia, boron, a halogen, mercury, mercury oxide, a compound thereof, a complex thereof, a salt thereof, an organic solvent, or a combination thereof, wherein the medium comprises a medium used in or obtained from a mining operation.

Embodiment 109 provides a method of extracting a target material from a medium, the method comprising:

contacting a copper zinc tin sulfur (CZTS) sorbent with the target material in the medium comprising the target material to form a used CZTS sorbent that comprises the target material, wherein the target material comprises a metal, a heavy metal, a precious metal, a rare earth metal, a rare metal, an alkali metal, a transition metal, an alkaline earth metal, a metalloid, selenium, selenite, selenate, sulfur, nitrogen, nitrogen dioxide, nitrate, nitrite, phosphorus, phosphate, phosphite, sulfur, sulfur dioxide, ammonia, boron, a halogen, mercury, mercury oxide, a compound thereof, a complex thereof, a salt thereof, an organic solvent, or a combination thereof, wherein the medium is a medium from a combustion or cleanup process in a power plant.

Embodiment 110 provides a method of forming a CZTS sorbent, the method comprising:

combining

-   -   copper, a compound thereof, or a salt thereof,     -   zinc, a compound thereof, or a salt thereof,     -   tin, a compound thereof, or a salt thereof, and     -   sulfur, a compound thereof, or a salt thereof,

to form a starting material mixture; and

processing the starting material mixture under conditions suitable to form the CZTS sorbent.

Embodiment 111 provides the method of Embodiment 110, wherein the processing comprises mixing the starting material mixture.

Embodiment 112 provides the method of any one of Embodiments 110-111, wherein the processing comprises heating the starting material mixture.

Embodiment 113 provides the method of any one or any combination of Embodiments 1-112 optionally configured such that all elements or options recited are available to use or select from. 

What is claimed is:
 1. A copper zinc tin sulfur (CZTS) material comprising: copper zinc tin sulfide having the formula Cu₂ZnSnS₄; wherein the CZTS material is a particulate and has a 50% volume-average particle size of 0.5 nm to 75 mm.
 2. The CZTS material of claim 1, wherein the CZTS material is a sorbent.
 3. The CZTS material of claim 1, wherein the CZTS material has a 50% volume-average particle size of 1 nm to 50 microns.
 4. The CZTS material of claim 1, wherein the CZTS material has a 50% volume-average particle size of 1 micron to 5 microns.
 5. The CZTS material of claim 1, wherein the Cu₂ZnSnS₄ comprises a kesterite structure.
 6. The CZTS material of claim 1, wherein the Cu₂ZnSnS₄ is in an alloyed form.
 7. The CZTS material of claim 1, wherein the Cu₂ZnSnS₄ is in an unalloyed form.
 8. The CZTS material of claim 1, wherein the Cu₂ZnSnS₄ is 0.001 wt % to 100 wt % of the CZTS material.
 9. The CZTS material of claim 1, wherein the Cu₂ZnSnS₄ is 0.001 wt % to 20 wt % of the CZTS material.
 10. The CZTS material of claim 1, wherein the Cu₂ZnSnS₄ is 80 wt % to 100 wt % of the CZTS material.
 11. The CZTS material of claim 1, wherein the CZTS material further comprises one or more elements, compounds thereof, or combinations thereof, in addition to copper, zinc, tin, and sulfur.
 12. The CZTS material of claim 1, wherein the CZTS material further comprises zinc, iron, aluminum, sulfur, selenium, a selenite, ferrous oxide, ferric oxide, or a combination thereof.
 13. The CZTS material of claim 1, wherein the CZTS material further comprises a metal, a carbon-based sorbent, a clay, zeolite, a hydroxide salt, or a combination thereof.
 14. The CZTS material of claim 1, wherein the CZTS material further comprises activated carbon, bentonite, zeolite, calcium hydroxide, or a combination thereof.
 15. The CZTS material of claim 1, wherein the CZTS material further comprises ZnS, CuS, Cu₂SnS₃, CuZn₂, SnS, or a combination thereof.
 16. The CZTS material of claim 15, wherein the ZnS, CuS, Cu₂SnS₃, CuZn₂, SnS, or a combination thereof, is 0.001 wt % to less than 100 wt % of the CZTS material.
 17. The CZTS material of claim 15, wherein the ZnS, CuS, Cu₂SnS₃, CuZn₂, SnS, or a combination thereof, is 0.001 wt % to 50 wt % of the CZTS material.
 18. The CZTS material of claim 1, wherein the CZTS material has a surface area of 0.2 m²/g to 2000 m²/g.
 19. The CZTS material of claim 1, wherein the CZTS material has a surface area of 1 m²/g to 50 m²/g.
 20. The CZTS material of claim 1, wherein the CZTS material has a density of 2 to 8 g/cm³.
 21. The CZTS material of claim 1, wherein the CZTS material has a density of 3 to 5 g/cm³.
 22. The CZTS material of claim 1, wherein the CZTS material is formed with a method comprising: heating a mixture comprising a copper salt, a zinc salt, a tin salt, and a sulfur compound.
 23. The CZTS material of claim 1, wherein the CZTS material is formed with a method comprising: heating a mixture comprising copper acetate monohydrate, zinc acetate dihydrate, tin chloride dihydrate, and thiourea.
 24. A method of forming a CZTS material, the method comprising: heating a mixture comprising a copper salt, a zinc salt, a tin salt, and a sulfur compound to form the CZTS material, the CZTS material comprising copper zinc tin sulfide having the formula Cu₂ZnSnS₄, wherein the CZTS material is a particulate and has a 50% volume-average particle size of 0.5 nm to 75 mm.
 25. The method of claim 24, wherein the copper salt comprises copper acetate monohydrate, the zinc salt comprises zinc acetate dihydrate, the tin salt comprises tin chloride dihydrate, and the sulfur compound comprises thiourea. 